Methods and systems for polymer deposition

ABSTRACT

Systems having one or more features that are advantageous for depositing fluorinated polymeric coatings on substrates, and methods of employing such systems to deposit such coatings, are generally provided.

FIELD

Systems and methods for depositing fluorinated polymers onto substratesare generally provided.

BACKGROUND

Chemical vapor deposition may be employed to deposit fluorinatedpolymeric coatings. However, some systems employed to perform suchprocesses may exhibit one or more drawbacks that result in unevencoatings, inconsistent coatings, and/or that require undesirablyfrequent repair and/or adjustment.

Accordingly, improved systems and methods for depositing fluorinatedpolymeric coating are needed.

SUMMARY

The present disclosure generally provides systems for depositingfluorinated polymeric coatings onto substrates related methods. Thesubject matter described herein involves, in some cases, interrelatedproducts, alternative solutions to a particular problem, and/or aplurality of different uses of one or more systems and/or articles.

In some embodiments, a system is provided. The system comprises adeposition chamber comprising a reaction volume and a cooling element.The reaction volume is capable of comprising hexafluoropropylene oxidevapor and being evacuated of air by a source of vacuum. The reactionvolume comprises a filament taking the form of a wire configured toincrease in temperature upon the application of a voltage thereto. Thewire is configured to heat the hexafluoropropylene oxide vapor, therebycausing it to decompose. A substrate is positioned in the reactionvolume. The cooling element is positioned around the substrate. Thecooling element extends from a bottom of the substrate to the top of thesubstrate.

In some embodiments, a system comprises a deposition chamber comprisinga reaction volume and a cooling element. The reaction volume is capableof comprising hexafluoropropylene oxide vapor and being evacuated of airby a source of vacuum. The reaction volume comprises a filament takingthe form of a wire configured to increase in temperature upon theapplication of a voltage thereto. The wire is configured to heat thehexafluoropropylene oxide vapor, thereby causing it to decompose. Asubstrate is positioned in the reaction volume. The cooling element ispositioned around the substrate. The substrate is freely-movable withrespect to the cooling element.

In some embodiments, a method is provided. The method comprisespolymerizing hexafluoropropylene oxide to form a particle comprisingpoly(tetrafluoroethylene) and depositing the particle comprisingpoly(tetrafluoroethylene) onto a surface. The polymerization isperformed in a reaction volume. The reaction volume is positioned in adeposition chamber. The reaction volume comprises at most 10 mTorr ofair and comprises hexafluoropropylene oxide vapor. The reaction volumecomprises a filament taking the form of a resistively heated wire. Thewire heats the hexafluoropropylene oxide vapor, thereby causing it todecompose. When the particle forms, it is surrounded by gas.

In some embodiments, a method comprises depositing a coating comprisingpoly(tetrafluoroethylene) on a substrate. The substrate is positioned ina reaction volume. The reaction volume is positioned in a depositionchamber. The reaction volume comprises at most 10 mTorr of air andcomprises hexafluoropropylene oxide vapor. The reaction volume comprisesa filament taking the form of a resistively heated wire. The wire heatsthe hexafluoropropylene oxide vapor, thereby causing it to decompose.The substrate outgasses one or more gases during the deposition of thecoating. The one or more gases make up greater than or equal to 0.1 mol% and less than or equal to 10 mol % of the gases present in thereaction volume during the deposition of the coating.

In some embodiments, a method comprises removing contaminants from asurface of a substrate by immersing the substrate in a solvent, and,within 30 minutes after the contaminants are removed, depositing acoating comprising poly(tetrafluoroethylene) onto the surface of thesubstrate by chemical vapor deposition. During the deposition step, thesubstrate is positioned in a reaction volume, the reaction volume ispositioned in a deposition chamber, the reaction volume comprises atmost 10 mTorr of air and comprises hexafluoropropylene oxide vapor, thereaction volume comprises a filament taking the form of a resistivelyheated wire, and the wire heats the hexafluoropropylene oxide vapor,thereby causing it to decompose. After the deposition step, the coatinghas an adhesion to the substrate such that its adhesion score, asdetermined by the procedure described in ASTM D3359, is greater than orequal to 4.

Other advantages and novel features of the present invention will becomeapparent from the following detailed description of various non-limitingembodiments of the invention when considered in conjunction with theaccompanying figures. In cases where the present specification and adocument incorporated by reference include conflicting and/orinconsistent disclosure, the present specification shall control. If twoor more documents incorporated by reference include conflicting and/orinconsistent disclosure with respect to each other, then the documenthaving the later effective date shall control.

BRIEF DESCRIPTION OF THE DRAWINGS

Non-limiting embodiments of the present invention will be described byway of example with reference to the accompanying figures, which areschematic and are not intended to be drawn to scale. In the figures,each identical or nearly identical component illustrated is typicallyrepresented by a single numeral. For purposes of clarity, not everycomponent is labeled in every figure, nor is every component of eachembodiment of the invention shown where illustration is not necessary toallow those of ordinary skill in the art to understand the invention. Inthe figures:

FIG. 1 shows a system comprising a deposition chamber and a reactionvolume, in accordance with some embodiments;

FIG. 2 shows a system comprising two sources, in accordance with someembodiments;

FIG. 3 shows a system comprising a filament, in accordance with someembodiments;

FIG. 4 shows a reaction occurring inside a reaction volume, inaccordance with some embodiments;

FIG. 5 shows a deposition process in which a polymer initially formed ina gas deposits onto a surface of a substrate and thereby coats thesubstrate, in accordance with some embodiments;

FIG. 6 shows a reaction volume enclosed by a plurality of walls and abase, in accordance with some embodiments;

FIG. 7 shows a reaction volume comprising a portion of a filament, inaccordance with some embodiments;

FIG. 8 shows a cooling element positioned around the substrate, inaccordance with some embodiments;

FIG. 9 shows a cooling element cooling element that has a height that istaller than the upper surface of the depressions in a substrate, inaccordance with some embodiments; and

FIG. 10 shows a reaction volume comprising a port, in accordance withsome embodiments.

DETAILED DESCRIPTION

Systems having one or more features that are advantageous for depositingfluorinated polymeric coatings on substrates, and methods of employingsuch systems to deposit such coatings, are generally provided. Somecomponents described herein have features that are advantageous whenprovided absent other components also described herein, and somecombinations of two or more components described herein interact in amanner to provide synergistic benefits to the system as a whole.

The systems described herein generally comprise a plurality ofcomponents that together allow a fluorinated polymeric coating to bedeposited on a substrate. These components typically include adeposition chamber comprising a reaction volume in which the fluorinatedpolymer is formed. FIG. 1 shows one non-limiting embodiment of a topview of a system having these components. In FIG. 1, the system 100comprises a deposition chamber 200 comprising a reaction volume 300.

A system may also comprise one or more sources that, when in fluidiccommunication with the reaction volume, may be configured to introduceone or more species into and/or remove one or more species from thereaction volume. FIG. 2 shows a system comprising two such sources: afirst source 402 and a second source 502. Each of the first and secondsources may independently be configured to introduce one or more speciesinto and/or remove one or more species from the reaction volume. Forinstance, in some embodiments, the first and/or second sources areconfigured to supply a reagent and/or combination of reagents to thereaction volume. The reagent(s) may be supplied in the presence of oneor more non-reactive species (e.g., a carrier gas, such as an inertcarrier gas) or may be provided as pure component(s). When two or morereagents are supplied, they may all be supplied together (e.g., in asingle, pre-mixed stream), they may all be supplied separately (e.g., inseparate streams), or there may exist at least one reagent that issupplied together with at least one other reagent and separately from atleast one other reagent.

As another example, in some embodiments, first and/or second sources areconfigured to allow and/or promote the removal of one or more speciesundesirable for inclusion in the reaction volume. The removal of suchspecies may be accomplished by removing all of the gaseous species inthe reaction volume together (e.g., the source may be a source ofvacuum). It is also possible for a system to be configured such that oneor more species are selectively removed from the reaction volume. Forinstance, a solid adsorbent may be configured to remove one or morespecies that adsorb thereon (e.g., water) but not remove one or morespecies that do not adsorb thereon.

It is also possible for a system to comprise further components thatpromote the reaction of any reagents introduced into the reactionvolume. As one example, in some embodiments, a system further comprisesa filament. It is also possible for a system to, additionally, oralternatively, comprise a source of plasma (e.g., a source ofradiofrequency plasma) and/or a lamp (e.g., an ultraviolet lamp). Whenpresent, the filament (and/or source of plasma and/or lamp) may beconfigured to and/or capable of providing energy, such as heat, to thereaction volume. This energy may initiate a reaction in the reactionvolume, such as a reaction that causes the deposition of a fluorinatedpolymeric coating on a substrate. It is also possible for energyprovided by a filament (and/or by another energy source), such as heat,to catalyze a reaction in the reaction volume. As one specific example,in some embodiments, the filament may comprise a wire that may heat amonomer, a precursor to a monomer, and/or an initiator. The heat maycause the monomer to undergo a polymerization reaction, may cause theprecursor to the monomer to decompose (e.g., into a monomer), and/or maycause the initiator to decompose (e.g., thereby activating it). Theheating may be accomplished by a variety of suitable manners, includingresistively. For example, the filament may be connected to a DC voltagesource and electrical ground.

In some embodiments, a system comprises a filament that takes the formof a wire. A potential difference may be established across the wire,causing current to flow from one end to the other and causing thefilament to heat due to resistive losses. In other words, a voltage maybe applied to the wire to increase its temperature and/or the wire maybe configured to increase in temperature upon the application of avoltage thereto. FIG. 3 shows one non-limiting embodiment of a systemcomprising a filament taking the form of a wire (labeled as element604). Although not shown in FIG. 3, systems may comprise two or morefilaments. Such filaments, if taking the form of wires, may comprisewires that are parallel to each other and/or may comprise wires that arenot parallel to each other. Similarly, such filaments may comprise wirespositioned at the same height with respect to the base of the reactionvolume and/or may comprise wires positioned at different heights withrespect to the base of the reaction volume.

As also not shown in FIG. 3, systems comprising a filament may furthercomprise one or more sources (e.g., like the sources shown in FIG. 2).Source(s) configured to introduce gases (e.g., monomers, precursors tomonomer, initiators, carrier gases) into the reaction volume may beconfigured to introduce gases such that they enter and/or flow throughthe reaction volume at a variety of angles to the filament. By way ofexample, if the filament takes the form of a wire, the source(s) may beconfigured to introduce the gases such that they enter and/or flowthrough the reaction volume in a direction parallel to the wire,perpendicular to the wire, or at any angle in between. In systemscomprising two or more sources, different sources may be configured tointroduce gases into the reaction volume into the reaction volume suchthat they enter and/or flow through the reaction volume in the samedirection and/or in different directions. Similarly, in systemscomprising two or more sources, different sources may be configured tointroduce gases into the reaction volume into the reaction volume suchthat they enter and/or flow through the reaction volume in the samelocation and/or in different locations. For instance, if a systemcomprises two or more sources and two or more filaments taking the formof wires, different sources may be configured to direct different gasestowards different wires.

It should be noted that, as described in further detail below somesources may be separated from a reaction volume by a port or anothersystem component. In such cases, the source itself may be configured tointroduce the gas in the relevant manner, the port or other systemcomponent may be configured to introduce the gas in the relevant manner,and/or the source and port or other system component may together beconfigured to introduce the gas in the relevant manner. In someembodiments, a source may be separated from the reaction volume by asystem component that is configured to split the gas provided by thesource into two or more streams and introduce at least some of thestreams into the reaction volume at different locations and/or such thatthey flow in different directions from each other.

Systems may also provide further components and/or components similar tothose shown in FIGS. 1-3 but differing in one or more ways. Furtherdetails regarding such system components are provided below.

As described elsewhere herein, the systems described herein may besuitable for depositing fluorinated polymeric coatings on a substrate.The fluorinated polymeric coatings may be formed in a reaction volumefrom fluorinated monomers introduced thereinto (e.g., by a source, by achemical reaction of a precursor to a monomer introduced thereinto).Once inside the reaction volume, the monomers may undergo apolymerization reaction to form the fluorinated polymer. FIG. 4 showsone example of a reaction incurring inside a reaction volume. In FIG. 4,two polymers 706 and 756 form in the reaction volume 306 from themonomers 806. Polymerization may occur at a variety of suitablelocations inside the reaction volume. In some embodiments, like theembodiment shown in FIG. 4, the polymerization occurs in an environmentsurrounded by gas (e.g., including gaseous monomer and/or one or morecarrier gases). It is also possible for the polymerization to occur on asurface (e.g., on a base and/or wall enclosing the reaction volume, on asubstrate being coated).

Polymers, if formed when surrounded by gas, may eventually deposit ontoa surface (e.g., of a substrate being coated) once they achievesufficient molecular weight to form a particle. FIG. 5 shows one exampleof a deposition process in which a polymer initially formed in a gas(e.g., surrounded on all sides by a gas) deposits onto a surface of asubstrate and thereby coats the substrate. In FIG. 5, the polymer 708has grown from the polymer 706 shown in FIG. 4 so that its molecularweight has increased by two monomers. This has caused the polymer 708 toform a particle that deposits from the gaseous environment in thereaction volume 308 onto the substrate 908. The polymer 758 has notincreased in molecular weight, and so it remains gaseous and does notdeposit onto the substrate 908.

It should also be understood that, in some embodiments, a polymer thatincreases in molecular weight may nucleate a particle that stayssuspended in a gaseous interior of a reaction volume for a period oftime before depositing onto a surface. The particle may serve as anucleation site for other polymer chains and/or other growing polymerchains may agglomerate with the particle. Once the resultant particle isof a sufficient size to no longer be suspended in the gaseousenvironment, it may deposit onto a surface (e.g., of a substrate beingcoated). Deposition that occurs in this manner may result in theformation of a coating that has a morphology comprising agglomeratedparticles.

Like for the systems described above, the processes for depositingpolymeric coatings on substrates may comprise one or more further stepsand/or differ from the processes described above in one or more ways.Having now provided an overview of an exemplary system that may beemployed to form fluorinated polymeric coatings and an exemplary processby which such coatings may be formed, further details regardingcomponents that may be employed in such exemplary systems and methodsthat such exemplary systems may be employed to perform are described infurther detail below.

As described elsewhere herein, in some embodiments, a system comprises areaction volume. The reaction volume may be enclosed by a plurality ofwalls and a base. FIG. 6 shows one non-limiting embodiment of across-section of a reaction volume having this property. In FIG. 6, thereaction volume 310 is enclosed by the walls 1010, 1040, and 1070 and bythe base 1110. The walls and the base may be the walls and the base of adeposition chamber in which the reaction volume is positioned. In otherwords, the deposition chamber may enclose the reaction volume and theinterior of the deposition chamber may be identical to the interior ofthe reaction volume. It is also possible for the walls and the baseenclosing the reaction volume to be positioned interior to thedeposition chamber. In other words, the deposition chamber may enclosethe walls and the base, and these walls and base may enclose thereaction volume. In such embodiments, the deposition chamber may furtherenclose other components of the system, such as portions of one or morefilaments not positioned in the reaction volume, portions of one or morecomponents of a cooling system not positioned in the reaction volume,motors, electrical components, and/or other system components notsuitable for inclusion in the reaction volume and/or that may beadvantageously excluded from the reaction volume.

In some embodiments, one or more of the walls and/or the base enclosinga reaction volume may be capable of undergoing one or more types ofmotion. For instance, in some embodiments, one, some, or all of thewalls may be moveable. As another example, the base may be movable. Itis also possible for a wall or a base to comprise one or more portionsthat are movable and one or more portions that are not movable. Movingone or more of the walls and/or the base (and/or one or more portionsthereof) may change the size of the reaction volume. By way of example,moving a wall and/or a base (and/or one or more portions thereof)towards the center of the reaction volume may make the reaction volumesmaller. Similarly, moving a wall and/or a base (and/or one or moreportions thereof) away from the center of the reaction volume may makethe reaction volume larger. When a wall and/or a base comprises two ormore portions that are movable, the portions may be movable separatelyfrom each other and/or may be movable together. The portions may bedirectly adjacent to each other or may be separated from each other byan unmovable portion. The movable portions may be next to each other, orone portion may be positioned around another portion (e.g., surroundingthe other portion on all sides, surrounding the other portion around amajority but not all of its edges).

The ability to adjust the size of the reaction volume may beadvantageous when it is desirable to use the system to deposit coatingsonto substrates having a variety of sizes. For instance, it may bedesirable to use a relatively small reaction volume to deposit a coatingonto a relatively small substrate, as this may minimize the amount ofreagent needed to form the coating and/or may promote the formation of arelatively large percentage of the deposited coating on the substrate(e.g., instead of the base and/or walls). As another example, it may benecessary to use a larger reaction volume to coat a larger substrate, asit is desirable for the reaction volume to be of sufficient size toenclose the substrate. As a third example, in some embodiments, it maybe desirable to change the size of the reaction volume when the reactionvolume is being used for different types of processes. For instance, itmay be desirable for the reaction volume to be smaller when the systemis being employed to perform smaller, testing runs. Later, duringproduction runs, it may be desirable to coat larger substrates and/ormore substrates during a single run, making a larger reaction volumedesirable. Employing the same reaction volume for both processes mayfacilitate maintaining similar reaction conditions during bothprocesses.

It is also possible that other advantages may flow from the ability toadjust the size of the reaction volume. For instance, in someembodiments, adjusting the reaction volume may cause one or morefeatures of the reaction(s) taking place therein to change, and so theability to adjust the size of a reaction volume may allow an operator toadjust one or more features of such reaction(s) and/or one or morefeatures of a fluorinated polymeric coating formed by such reaction(s)(e.g., its morphology, molecular weight, uniformity, and/orconformality). As one example, adjusting the reaction volume by movingthe base upwards may bring the base closer to the portion(s) of thefilament(s) positioned inside the reaction volume, which may affect anyreaction(s) catalyzed by the heat provided by the filament(s).Accordingly, the ability to adjust the size of the reaction volume in arelatively facile, rapid, and/or economic manner may advantageouslyallow an operator to adjust reaction conditions in such a manner.

In some embodiments, a base and/or a portion of a base may be rotatable.It is also possible for a base to comprise one or more portions that arerotatable and one or more portions that are not rotatable. When a basecomprises two or more portions that are rotatable, the portions may berotatable separately from each other (e.g., at different points in time)and/or may be rotatable together (e.g., simultaneously). The portionsmay be directly adjacent to each other or may be separated from eachother by an unrotatable portion. The portions may be next to each other,or one portion may be positioned around another portion (e.g.,surrounding the other portion on all sides, surrounding the otherportion around a majority but not all of its edges).

When a base and/or a portion of a base is rotatable, the axis ofrotation may generally be selected as desired. In some embodiments, theaxis of rotation is perpendicular to the base and/or the rotatableportion of the base. The axis of rotation may pass through the center ofthe base and/or the rotatable portion thereof, or may be off-center.

Without wishing to be bound by any particular theory, it is believedthat rotating the base (and/or a portion thereof) may advantageouslypromote the deposition of a uniform coating on a substrate positioned onthe base and/or uniform coatings on a plurality of substrates positionedon the base. As the base (and/or portion thereof) rotates, it may moveany substrate(s) positioned thereon in an arc about the axis ofrotation, which may exposing the substrate(s) sequentially to differentportions of the reaction volume. If some portions of the reaction volumediffer from one another such that the fluorinated polymer being formedtherein differs, such rotation may substantially reduce and/or preventthe deposition of a coating that varies across the substrate and/orsubstrates. By way of example, as a substrate is moved through thereaction volume by the rotation of the base, it (and its portions) maybe exposed sequentially to these differing portions of the reactionvolume and may accumulate a coating comprising a fluorinated polymer inthese differing portions of the reaction volume. The resultant coatingin each portion of the substrate may be an “average” of coating beingformed at the various locations in the reaction volume, and so thecoating as a whole may be uniform even if the reaction from which itforms varies across the reaction volume.

A rotatable base may be capable of undergoing a variety of differenttypes of rotation. In some embodiments, the rotatable base is onlycapable of rotating in one direction (e.g., clockwise,counterclockwise). It is also possible for a rotatable base to beconfigured to rotate in only one direction. For instance, the system maycomprise software that instructs the base to only rotate in onedirection. In some embodiments, the base may be capable of and/orconfigured to rotate continuously (e.g., for a set period of time,indefinitely) and/or without operator intervention. As one example, abase may be provided with software that can rotate the base autonomouslywithout active operator involvement.

A rotatable base may be capable of rotating at a variety of suitablerates. In some embodiments, the rate of rotation is selected such that,over the course of a deposition process performed in a reaction volume,the rotatable base undergoes exactly one complete rotation or undergoesan integer multiple of complete rotations. In some embodiments, the rateof rotation is greater than or equal to 0.1 rpm, greater than or equalto 0.2 rpm, greater than or equal to 0.5 rpm, greater than or equal to0.75 rpm, greater than or equal to 1 rpm, greater than or equal to 2rpm, greater than or equal to 5 rpm, or greater than or equal to 7.5rpm. In some embodiments, the rate of rotation is less than or equal to10 rpm, less than or equal to 7.5 rpm, less than or equal to 5 rpm, lessthan or equal to 2 rpm, less than or equal to 1 rpm, less than or equalto 0.75 rpm, less than or equal to 0.5 rpm, or less than or equal to 0.2rpm. Combinations of the above-referenced ranges are also possible(e.g., greater than or equal to 0.1 rpm and less than or equal to 10rpm). Other ranges are also possible.

In some embodiments, a system is configured such that one or more of thewalls and/or the base of the reaction volume are capable of beingremoved and/or replaced. It is also possible for one or more wallsand/or the base to comprise one or more portions that are capable ofbeing removed and/or replaced and to comprise one or more portions thatare incapable of being removed and/or replaced. As one example, in someembodiments, a system is configured such that the base and/or a portionof the base is removable. This may be desirable for embodiments in whichit is advantageous to use different types of bases for different typesof processes. For instance, in some embodiments, it may be desirable tobe able to reversibly switch between a rotating base and a non-rotatingbase. When a base and/or walls are removable, they may be configured tobe removed and/or replaced relatively quickly. For instance, in someembodiments, one wall may be replaced with another and/or one base maybe replaced with another over a period of seconds and/or minutes.

In some embodiments, a system comprises a base (e.g., a rotatable base,a non-rotatable base) and/or one or more walls that is capable of beingheated, cooled, and/or maintained at a temperature within a particularrange. For instance, a base and/or one or more of the walls that enclosea reaction volume may be capable of being heated, cooled, and/ormaintained at a temperature within a particular range. As anotherexample, a base and/or one or more of the walls of a deposition chamber(e.g., a deposition chamber enclosing a base and one or more walls thatenclose a reaction volume) may be capable of being heated, cooled,and/or maintained at a temperature within a particular range. In someembodiments, the base and/or wall(s) may be in thermal communicationwith a cooling system and/or a heating system. For instance, the baseand/or wall(s) may be cooled and/or heated by flowing a cooled and/orheated fluid across a surface of the base and/or (wall(s) (e.g., asurface opposite a surface on which a substrate is positioned) and/orthrough the interior of the base and/or wall(s). One example of asuitable fluid for this purpose is water. In some embodiments, the baseand/or wall(s) may be cooled and/or heated electrically. For instance,the base and/or wall(s) may be resistively heated. As another example,heat may be provided to the base and/or wall(s) and/or removed from thebase and/or wall(s) by use of Peltier cooling system.

It should also be noted that the base and/or wall(s) may be directlyheated and/or cooled, and/or may be indirectly heated and/or cooled.Direct heating and/or cooling may comprise heating and/or cooling thebase and/or walls directly by one or more of the methods described inthe preceding paragraph. Indirectly heating and/or cooling may comprisedirectly heating and/or cooling an article other than the base or wallsby one or more of the methods described in the preceding paragraph, andcontacting the base and/or walls with the directly-heated and/or -cooledarticle.

It should be noted that it is also possible for a cooling element to bedisposed on the base, an embodiment that is described further elsewhereherein. In other words, in some embodiments the base itself is heatedand/or cooled and no further cooling element is provided, in someembodiments the base itself is neither heated nor cooled and a coolingelement is disposed on the base to cool a substrate positioned thereon,in some embodiments the base itself is heated and/or cooled and afurther cooling element is disposed on the base to cool a substratepositioned thereon, and in some embodiments the base is neither heatednor cooled and no cooling element is provided.

In some embodiments, the walls and the base enclose the reaction volumesuch that the reaction volume is not in fluidic communication with anenvironment exterior to the reaction volume. The reaction volume may beisolated in this manner at some points in time, but not others. Forinstance, the reaction volume may be isolated in this manner when influidic communication with a source of vacuum and/or during a reaction(e.g., a polymerization reaction) performed in the reaction volume. Theisolation of the reaction volume may be accomplished by employing aplurality of walls and a base that are gas-tight and that are joined bygas-tight connections. In some embodiments, the isolation of thereaction volume is accomplished (and/or gas transport out of thereaction volume is reduced) by introducing gas into the reaction volumein a manner such that it is directed away from any openings and/orpotential sources of gas leakage.

As described elsewhere herein, in some embodiments, a filament and/orplurality of filaments passes through a reaction volume. The filament(s)may be entirely contained within the reaction volume and/or may comprisesome portions that are outside of the reaction volume. Similarly, thefilament(s) may be entirely contained within the deposition chamberand/or may comprise some portions that are outside of the depositionchamber.

In some embodiments, a filament and/or plurality of filaments ispositioned such that the filament(s) can be moved facilely from onelocation to another. As an example, in some embodiments, a system may beconfigured such that the filament can be positioned at two or morediscrete locations inside a reaction volume and/or can be moved betweentwo or more discrete locations inside the reaction volume in arelatively easy manner. For instance, in some embodiments, there may betwo or more stable locations inside the reaction volume at which thefilament may be positioned, and one or more unstable locations betweenthe two or more stable locations. The filament may be incapable of beingpositioned stably at the unstable location(s). For instance, withreference to FIG. 7, a filament 612 may be capable of being positionedstably at the stable locations 1212 and 1262 but incapable of beingstably positioned at the unstable location 1312 positioned between thetwo stable locations 1212 and 1262. FIG. 7 shows a cross-sectional viewof a reaction volume 312.

A filament that is positioned stably at a location may be positionedsuch that, absent the application of a force to the filament by anoperator, it may remain in that location indefinitely. In someembodiments, a filament is positioned stably at a location such that,after undergoing a small perturbation that removes it from the location,it returns to the location without any additional force applied by theoperator. It is also possible for a filament to be positioned stably ata location such that it remains there even under the application offorces having small values applied by an operator.

A filament that is positioned unstably at a location may be positionedsuch that, absent the application of a force to the filament by theoperator, it translates from that location to another location (e.g., toa location at which it is stably positioned). In some embodiments, afilament is positioned unstably at a location such that, afterundergoing a small perturbation that removes it from that location, ittranslates to another location (e.g., to a location at which it isstably positioned) and/or does not return to the location at which itwas previously unstably positioned. It is also possible for a filamentto be positioned unstably at a location such that it will not remainthere even under the application of forces having small values appliedby an operator.

Without wishing to be bound by any particular theory, it is believedthat limiting the stable positions of a filament to one or more definedand/or pre-determined locations may be advantageous. For instance, it isbelieved that this property may allow operators to employ the system ina relatively predictable and/or reproducible manner. As an example, anoperator may initially position the filament(s) such that they arelocated at one or more of the stable location(s). Then, the operator mayuse the system to deposit a fluorinated polymer while the filament(s)are positioned at the same stable location(s). The stability of thelocations may allow the operator to have good control over the positionof the filament because the operator may be able to trust that thefilament(s) do not move after initial placement. Additionally, in someembodiments, the filament(s) may be retained at their stable location(s)between uses of the system. This may assist an operator with employingthe system such that it has the same, unaltered configuration duringmultiple sequential runs. As a third example, in some embodiments, anoperator may use consistent but differing stable location(s) fordifferent processes. For instance, an operator may employ one stablelocation for one type of substrate to be coated and another, differentstable location for coating a second, different type of substrate. Theoperator (and/or software provided with the system) may take note of thedifferent stable locations employed and may select the appropriate andreproducible stable location for a substrate after it has been loaded.

In some embodiments, a system comprises a racking system that assistswith defining stable and unstable locations for one or more filament(s)at least partially positioned inside a reaction volume. The rackingsystem may be configured such that it can has certain stableconfigurations and certain unstable configurations (e.g., positionedbetween the stable configurations). As an example, in some embodiments,a racking system may comprise gears, a ratchet and pawl combination,stationary filament supports (e.g., slots, clamps, etc.), and/or anothercomponent and/or combination of components that together may cause thisresult. In some embodiments, the racking system is configured such thatthe stable locations for the filaments are separated by a uniformdistance. In other words, the filament(s) may be capable of beingpositioned at a plurality of stable locations, and the distance betweeneach stable location and its nearest neighbor may be relatively uniform.

When present, stable locations for filament(s) may be separated by avariety of suitable average distances. In some embodiments, the stablelocations are separated by an average distance of greater than or equalto 0.1 mm, greater than or equal to 0.2 mm, greater than or equal to 0.5mm, greater than or equal to 0.75 mm, greater than or equal to 1 mm,greater than or equal to 2 mm, greater than or equal to 5 mm, greaterthan or equal to 7.5 mm, greater than or equal to 10 mm, greater than orequal to 20 mm, greater than or equal to 50 mm, or greater than or equalto 75 mm. In some embodiments, the stable locations are separated by anaverage distance of less than or equal to 100 mm, less than or equal to75 mm, less than or equal to 50 mm, less than or equal to 20 mm, lessthan or equal to 10 mm, less than or equal to 7.5 mm, less than or equalto 5 mm, less than or equal to 2 mm, less than or equal to 1 mm, lessthan or equal to 0.75 mm, less than or equal to 0.5 mm, or less than orequal to 0.2 mm. Combinations of the above-referenced ranges are alsopossible (e.g., greater than or equal to 0.1 mm and less than or equalto 100 mm, or greater than or equal to 2 mm and less than or equal to 10mm). Other ranges are also possible.

In some embodiments, a filament and/or plurality of filaments may beprepared for use prior to be positioned at least partially in a reactionvolume. Preparing the filaments for use prior to actual use may reducethe system downtime that would otherwise accrue as the filaments areprepared. One example of a manner in which a filament and/or pluralityof filaments may be prepared for use is that, if such filament(s) takethe form of wire(s), they may be pre-strung on a filament support (e.g.,a racking system as described elsewhere herein) prior to beingintroduced into the reaction volume. The pre-strung filament support maythen be introduced into the reaction volume in one piece, instead ofintroducing and stringing each filament separately. Additionally, whenan operator wishes to remove the filaments from the system (e.g., to bereplaced with other filaments), it may be possible for the operator todo so by removing the filament support instead of removing each filamentindividually. This may further reduce equipment downtime.

When a system comprises a plurality of filaments taking the form ofwires, the wires may be positioned at advantageous distances from theirnearest neighbors. In some embodiments, an average distance between eachwire and its nearest neighbor may be greater than or equal to 0.1 inch,greater than or equal to 0.25 inches, greater than or equal to 0.5inches, greater than or equal to 0.75 inches, greater than or equal to 1inch, greater than or equal to 1.25 inches, greater than or equal to 1.5inches, greater than or equal to 1.75 inches, greater than or equal to 2inches, or greater than or equal to 2.25 inches. In some embodiments, anaverage distance between each wire and its nearest neighbor may be lessthan or equal to 2.5 inches, less than or equal to 2.25 inches, lessthan or equal to 2 inches, less than or equal to 1.75 inches, less thanor equal to 1.5 inches, less than or equal to 1.25 inches, less than orequal to 1 inch, less than or equal to 0.75 inches, less than or equalto 0.5 inches, or less than or equal to 0.25 inches. Combinations of theabove-referenced ranges are also possible (e.g., greater than or equalto 0.1 inch and less than or equal to 2.5 inches). Other ranges are alsopossible.

In some embodiments, each wire in a plurality of wires may be positionedat a distance from its nearest neighbor that is substantially the same(e.g., the standard deviation of the distance between each wire and itsnearest neighbor may be less than or equal to 10%, less than or equal to5%, less than or equal to 2%, or less than or equal to 1% of the averagedistance between the each filament and its nearest neighbor). In someembodiments, different wires in the plurality of wires may be positionedat substantially different distances from their nearest neighbors.

When a system comprises a plurality of filaments taking the form ofwires at least partially in a reaction volume, the wires may bepositioned at advantageous distances from the base that (together with aplurality of walls) encloses the reaction volume. The average distancebetween the wires and the base may be greater than or equal to 0.1 inch,greater than or equal to 0.2 inches, greater than or equal to 0.25inches, greater than or equal to 0.3 inches, greater than or equal to0.4 inches, greater than or equal to 0.5 inches, greater than or equalto 0.75 inches, greater than or equal to 1 inch, greater than or equalto 1.5 inches, greater than or equal to 2 inches, greater than or equalto 3 inches, greater than or equal to 4 inches, greater than or equal to5 inches, greater than or equal to 7.5 inches, greater than or equal to10 inches, greater than or equal to 12.5 inches, greater than or equalto 15 inches, greater than or equal to 17.5 inches, or greater than orequal to 20 inches. The average distance between the wires and the basemay be less than or equal to 24 inches, less than or equal to 20 inches,less than or equal to 17.5 inches, less than or equal to 15 inches, lessthan or equal to 12.5 inches, less than or equal to 10 inches, less thanor equal to 7.5 inches, less than or equal to 5 inches, less than orequal to 4 inches, less than or equal to 3 inches, less than or equal to2 inches, less than or equal to 1.5 inches, less than or equal to 1inch, less than or equal to 0.75 inches, less than or equal to 0.5inches, less than or equal to 0.4 inches, less than or equal to 0.3inches, less than or equal to 0.25 inches, or less than or equal to 0.2inches. Combinations of the above-referenced ranges are also possible(e.g., greater than or equal to 0.1 inch and less than or equal to 24inches, or greater than or equal to 0.25 inches and less than or equalto 5 inches). Other ranges are also possible.

In some embodiments, each wire in a plurality of wires is positioned ata distance from the base that is substantially the same (e.g., thestandard deviation of the distance between each wire and the base may beless than or equal to 10%, less than or equal to 5%, less than or equalto 2%, or less than or equal to 1% of the average distance between theeach filament and the base). In some embodiments, different wires in theplurality of wires are positioned at substantially different distancesfrom the base.

As described elsewhere herein, in some embodiments, the system isconfigured such that the distance between a wire (and/or plurality ofwires) and a base may be changed. The change may comprise adjusting thedistance from one of the values in the above-referenced ranges to asecond, different value in one or more of the above-referenced ranges.This change may occur relatively rapidly. As one example, in someembodiments, the system may be configured such that the distance betweenthe wire (and/or plurality of wires) and the base may be changed over aperiod of time of seconds or minutes.

In some embodiments, one or more processes may be performed onfilaments. As an example, in some embodiments, and as describedelsewhere herein, a voltage is applied across a filament (e.g., across afilament taking the form of a wire) to cause it to resistively heat. Insome embodiments, the application of a voltage across a filament causesthe filament to be heated to a temperature that is desirable. Forinstance, application of a voltage across a filament may cause thefilament to be heated to a temperature of greater than or equal to 150°C., greater than or equal to 200° C., greater than or equal to 250° C.,greater than or equal to 300° C., greater than or equal to 350° C.,greater than or equal to 400° C., greater than or equal to 450° C.,greater than or equal to 500° C., greater than or equal to 550° C.,greater than or equal to 600° C., greater than or equal to 650° C.,greater than or equal to 700° C., greater than or equal to 750° C.,greater than or equal to 800° C., greater than or equal to 850° C.,greater than or equal to 900° C., greater than or equal to 950° C.,greater than or equal to 1000° C., greater than or equal to 1100° C.,greater than or equal to 1200° C., greater than or equal to 1300° C., orgreater than or equal to 1400° C. In some embodiments, application of avoltage across a filament causes the filament to be heated to atemperature of less than or equal to 1500° C., less than or equal to1400° C., less than or equal to 1300° C., less than or equal to 1200°C., less than or equal to 1100° C., less than or equal to 1000° C., lessthan or equal to 950° C., less than or equal to 900° C., less than orequal to 850° C., less than or equal to 800° C., less than or equal to750° C., less than or equal to 700° C., less than or equal to 650° C.,less than or equal to 600° C., less than or equal to 550° C., less thanor equal to 500° C., less than or equal to 450° C., less than or equalto 400° C., less than or equal to 350° C., less than or equal to 300°C., less than or equal to 250° C., or less than or equal to 200° C.Combinations of the above-referenced ranges are also possible (e.g.,greater than or equal to 150° C. and less than or equal to 1500° C., orgreater than or equal to 150° C. and less than or equal to 1000° C.).Other ranges are also possible. The temperature of the filament may bedetermined by use of a thermocouple.

It is also possible for the voltage applied across a filament and/or forthe temperature of a filament to be maintained within a certain range.This range may be a range that enhances the rate of one or moredesirable reactions and/or reduces the rate of one or more undesirablereactions. For instance, in the case of a polymerization reaction, thetemperature range may be a range that promotes polymerization of thedesired monomers at appreciable rates, promotes the decomposition ofprecursor(s) to form initiator(s) at appreciable rates, and/or promotesthe decomposition of precursor(s) to form the desired monomer(s) atappreciable rates but which does not promote undesirable side reactionsto a significant extent. The temperature range of the filament may, insome embodiments, be maintained within a particular range by anautomated process. The automated process may comprise sensing thetemperature of the filament (and/or sensing a property of the filamentand/or reaction volume that is a proxy for the temperature of thefilament). It may also comprise adjusting one or more inputs to thefilament (and/or one or more properties of the reaction volume) if thetemperature of the filament (and/or its proxy) exceeds or falls below acertain range. If the temperature of the filament (and/or its proxy)falls within the range, the input(s) to the filament (and/or propertiesof the reaction volume) may be maintained.

As one specific example, in some embodiments, a temperature of afilament is maintained within a certain range by sensing and adjustingthe current passing through a resistively-heated filament. The energydissipated by the filament may have a known relationship to the currentpassing through the filament and the voltage applied across thefilament. For instance, the energy dissipated by the filament may becalculated by solving the following equation:Energy=(Current)*(Voltage). The temperature of the filament may bedetermined by solving the following equation: Resistivity ofFilament=(Resistivity at Reference Temperature)+(Known Variation ofResistivity with Temperature)*(Difference Between Reference Temperatureand Filament Temperature).

More specifically, in some embodiments, the temperature of a filament ismaintained within a certain temperature range by passing a currentthrough the filament, sensing the resistance of the filament, andadjusting the voltage applied across the filament if its measuredresistance differs by more than a certain percentage from a set point.The resistance of the filament may be sensed directly, or may be sensedindirectly (e.g., by sensing a proxy for the resistance and thendetermining the resistance from this proxy). One example of a method ofindirectly sensing the resistance of the filament comprises sensing thecurrent passing through the filament and then applying Ohm's law todetermine the resistance of the filament. The current passing throughthe filament may be determined by, for instance, use of an ammeter. Thevoltage may be adjusted to bring the current back to being within arange that is indicative of the filament being within a certaintemperature range. For instance, the voltage may be increased if a lowlevel of current is sensed flowing through the filament or the voltagemay be decreased if a high level of current is sensed flowing throughthe filament.

Adjustments to one or more filament properties may be made by aproportional-integral-derivative controller. The proportional-integralderivative controller may take as inputs any suitable properties thatare sensed and/or whose values may trigger an adjustment to the appliedvoltage. For instance, if the current passing through the filament issensed and/or the applied voltage is adjusted based on the currentpassing through the filament, the proportional-integral-derivativecontroller may adjust the voltage based on the sensed current. Asanother example, if the resistance of the filament is sensed and/or theapplied voltage is adjusted based on the resistance of the filament, theproportional-integral-derivative controller may adjust the voltage basedon the resistance of the filament (and, thus, on the voltage applied tothe filament and the current passing through the filament if Ohm's lawis employed to calculate this resistance). As a third example, if thepower dissipated by the filament is sensed and/or the applied voltage isadjusted based on the power dissipated by the filament, theproportional-integral-derivative controller may adjust the voltage basedon the power dissipated by the filament (and, thus, on the voltageapplied to the filament and the current passing through the filament ifthe equation for energy dissipation supplied above is employed tocalculate this resistance).

An adjustment to the voltage applied across the filament may be madewhen the resistance of the filament differs from the set point bygreater than or equal to 0.1% of the set point, greater than or equal to0.2% of the set point, greater than or equal to 0.5% of the set point,greater than or equal to 0.75% of the set point, greater than or equalto 1% of the set point, greater than or equal to 1.5% of the set point,greater than or equal to 2% of the set point, greater than or equal to2.5% of the set point, greater than or equal to 3% of the set point, orgreater than or equal to 4% of the set point. An adjustment to thevoltage applied across the filament may be made when the resistance ofthe filament differs from the set point by less than or equal to 5% ofthe set point, less than or equal to 4% of the set point, less than orequal to 3% of the set point, less than or equal to 2.5% of the setpoint, less than or equal to 2% of the set point, less than or equal to1.5% of the set point, less than or equal to 1% of the set point, lessthan or equal to 0.75% of the set point, less than or equal to 0.5% ofthe set point, or less than or equal to 0.2% of the set point.Combinations of the above-referenced ranges are also possible (e.g.,greater than or equal to 0.1% of the set point and less than or equal to5% of the set point, or greater than or equal to 0.1% of the set pointand less than or equal to 1.5% of the set point). Other ranges are alsopossible.

It should be understood that the ranges in the preceding paragraph mayindependently refer to values in excess of the set point or values belowthe set point. As an example, the reference to the adjustment of thevoltage applied across a filament at a variation of greater than orequal to 1% of the set point above may independently refer to theadjustment of the voltage applied across a filament when the resistanceof the filament is greater than or equal to 101% of the set point andthe adjustment of the voltage applied across a filament when theresistance of the filament is less than or equal to 99% of the setpoint. It is possible for the adjustment of the voltage applied across afilament to be triggered at positive and negative deviations of theresistance from the set point having the same absolute value (e.g., anadjustment of the voltage applied across a filament may be triggeredwhen the resistance of the filament exceeds the set point by greaterthan or equal to 1% of the set point or is reduced from the set point bygreater than or equal to 1% of the set point) or may be triggered atpositive and negative deviations of the resistance from the set pointhaving different values (e.g., an adjustment of the voltage appliedacross a filament may be triggered when the resistance of the filamentexceeds the set point by greater than or equal to 0.5% of the set pointor is reduced from the set point by greater than or equal to 1% of theset point).

It is also possible for a system to comprise a safety feature that shutsoff filament heating and/or the application of a voltage across afilament. One example of a safety feature is a feature that preventsfilament heating and/or the application of a voltage across the filamentwhen the reaction volume is open, advantageously preventing operatorsfrom touching a live filament. It is also possible for a safety featureto be a feature that prevents runaway heating of the filament and/or theapplication of a voltage across a filament that is broken and/orsubstantially weakened. For instance, in some embodiments, an automatedprocess for sensing the temperature of a filament (and/or sensing aproperty of the filament and/or reaction volume that is a proxy for thetemperature of the filament) may be performed as described in thepreceding paragraphs. If the temperature of the filament and/or proxyfor the temperature of the filament is outside of a certain range (e.g.,a range larger than the range at which an adjustment to an input to thefilament and/or a property of the reaction may be performed), a warningmay be provided and/or the filament may be turned off (e.g., by removingthe voltage applied thereacross). It is also possible for a warning tobe provided and/or for the filament to be turned off if a particular setof adjustments to the input(s) to the filament (and/or properties of thereaction volume) does not, after an appropriate period of time, resultin a change in the filament temperature and/or the proxy for thefilament temperature in a manner indicative of a return of the filamenttemperature to the desired range.

As another example, in some embodiments, an automated process forsensing the resistance of a filament (and/or sensing a property of thefilament and/or reaction volume that is a proxy for the resistance ofthe filament) may be performed as described in the preceding paragraphs.If the resistance of the filament and/or proxy for the resistance of thefilament is outside of a certain range (e.g., a range larger than therange at which an adjustment to an input to the filament and/or aproperty of the reaction may be performed), a warning may be providedand/or the filament may be turned off (e.g., by removing the voltageapplied thereacross). It is also possible for a warning to be providedand/or for the filament to be turned off if a particular set ofadjustments to the input(s) to the filament (and/or properties of thereaction volume) does not, after an appropriate period of time, resultin a change in the filament resistance and/or the proxy for the filamenttemperature in a manner indicative of a return of the filamentresistance to the desired range.

In some embodiments, the current passing through a filament may be aproxy for the temperature and/or the resistance of the filament. Asdescribed above, the current passing through a filament may also beemployed to determine the temperature of the filament. Additionally, andwithout wishing to be bound by any particular theory, it is believedthat the current passing through a filament upon the application of aknown voltage may be indicative of the resistance of the filament. Forinstance, by applying Ohm's law, the resistance of a filament may befound to be equal to the ratio of the applied voltage to the currentpassing through this filament. Accordingly, large changes in theresistance of a filament, rapid changes in the resistance of a filament,and/or changes in the resistance of a filament that do not respond to achange in the voltage applied across the filament may be indicative of afilament that has undergone a physical and/or chemical process causingit to have a different resistivity. If the filament's resistivitybecomes very high, the filament may undesirably dissipate large amountsof heat to the reaction volume, melt, and/or undergo catastrophicfailure (the latter of which may be sensed as the filament exhibitinginfinite resistance). For these reasons, the presence of a system thatwarns an operator that the filament may have undergone such a processand/or shuts off the filament may promote the safe operation of thesystem.

A warning may be provided and/or a filament may be shut off when theresistance of the filament differs from the set point by greater than orequal to 0.1% of the set point, greater than or equal to 0.2% of the setpoint, greater than or equal to 0.5% of the set point, greater than orequal to 0.75% of the set point, greater than or equal to 1% of the setpoint, greater than or equal to 1.5% of the set point, greater than orequal to 2% of the set point, greater than or equal to 2.5% of the setpoint, greater than or equal to 3% of the set point, or greater than orequal to 4% of the set point. A warning may be provided and/or afilament may be shut off when the resistance of the filament differsfrom the set point by less than or equal to 5% of the set point, lessthan or equal to 4% of the set point, less than or equal to 3% of theset point, less than or equal to 2.5% of the set point, less than orequal to 2% of the set point, less than or equal to 1.5% of the setpoint, less than or equal to 1% of the set point, less than or equal to0.75% of the set point, less than or equal to 0.5% of the set point, orless than or equal to 0.2% of the set point. Combinations of theabove-referenced ranges are also possible (e.g., greater than or equalto 0.1% of the set point and less than or equal to 5% of the set point,or greater than or equal to 0.1% of the set point and less than or equalto 1.5% of the set point). Other ranges are also possible.

It should be understood that the ranges in the preceding paragraph mayindependently refer to values in excess of the set point or values belowthe set point. As an example, the reference to the issuance of a warningat a variation of greater than or equal to 1% of the set point above mayindependently refer to the issuance of a warning when the resistance ofthe filament is greater than or equal to 101% of the set point and theissuance of a warning when the resistance of the filament is less thanor equal to 99% of the set point. It is possible for a warning to betriggered at positive and negative deviations of the resistance from theset point having the same absolute value (e.g., a warning may betriggered when the resistance of the filament exceeds the set point bygreater than or equal to 1% of the set point or is reduced from the setpoint by greater than or equal to 1% of the set point) or may betriggered at positive and negative deviations of the resistance from theset point having different values (e.g., a warning may be triggered whenthe resistance of the filament exceeds the set point by greater than orequal to 0.5% of the set point or is reduced from the set point bygreater than or equal to 1% of the set point).

It is also possible for a property of the filament other than itsresistance to be sensed and/or for an action to be taken by the system(e.g., an increase or decrease in the voltage applied across thefilament, a shutoff of the filament, the issuance of a warning) inresponse to a change in the value of a property other than resistanceand/or upon the sensing of a property other than resistance outside of arange around a set point. As one example, filament temperature (e.g., asdetermined by use of a pyrometer) may be sensed and/or one or moreactions may be taken by the system based, at least in part, on thesensed temperature. As another example, the power dissipated by thefilament may be sensed and/or one or more actions may be taken by thesystem based, at least in part, on the power dissipated as sensed.

Another example of a process that may be performed on a filament toincrease its performance is the application of a force to the filament.For instance, in some embodiments, a tensile force is applied to afilament taking the form of a wire. Without wishing to be bound by anyparticular theory, the application of the tensile force to the wire maycause the wire to become taut, which may prevent it from sagging and/ormay maintain the wire (e.g., stably) in a desirable position within thereaction volume. As sagging of the wire may undesirably cause the wireto break and/or form a short circuit upon contact with another componentpositioned in the reaction volume, keeping the wire taut mayadvantageously enhance system performance. The amount of force that isapplied may be selected based on one or more mechanical properties ofthe wire. As an example, the force may be selected such that it issufficient to pull the wire taut but not insufficient to break and/orcause appreciable elastic deformation of the wire.

In some embodiments, a ratio of the tensile force applied to the wire tothe rated tensile strength of the material forming the wire is greaterthan or equal to 0.1, greater than or equal to 0.15, greater than orequal to 0.2, greater than or equal to 0.25, greater than or equal to0.3, greater than or equal to 0.35, greater than or equal to 0.4,greater than or equal to 0.45, greater than or equal to 0.5, greaterthan or equal to 0.55, greater than or equal to 0.6, greater than orequal to 0.65, greater than or equal to 0.7, greater than or equal to0.75, greater than or equal to 0.8, greater than or equal to 0.85, orgreater than or equal to 0.9. In some embodiments, a ratio of thetensile force applied to the wire to the rated tensile strength of thematerial forming the wire is less than or equal to 0.95, less than orequal to 0.9, less than or equal to 0.85, less than or equal to 0.8,less than or equal to 0.75, less than or equal to 0.7, less than orequal to 0.65, less than or equal to 0.6, less than or equal to 0.55,less than or equal to 0.5, less than or equal to 0.45, less than orequal to 0.4, less than or equal to 0.35, less than or equal to 0.3,less than or equal to 0.25, less than or equal to 0.2, or less than orequal to 0.15. Combinations of the above-referenced ranges are alsopossible (e.g., greater than or equal to 0.1 and less than or equal to0.95, or greater than or equal to 0.6 and less than or equal to 0.8).Other ranges are also possible.

The values in the preceding paragraph may refer to the rated strength ofthe material forming the wire at a variety of suitable temperatures. Insome embodiments, the ratio of the tensile force applied to a wire toits rated tensile strength is in one or more of the ranges describedabove when the temperature of the wire is a temperature to which thefilament is heated during deposition of a fluorinated polymeric coating(e.g., a temperature in one or more such ranges provided elsewhereherein). Similarly, the amounts of tensile force may be applied to thewire when the wire is positioned in a variety of suitable environments.As an example, in some embodiments, the tensile force may be applied tothe wire during the deposition of a fluorinated polymeric coating on asubstrate. In such embodiments, the temperature and/or pressure of theenvironment in which the wire is positioned may be in one or more of theranges described for such deposition reactions elsewhere herein.

As described elsewhere herein, in some embodiments, energy may beprovided to a reaction volume by a plasma. This energy may catalyze oneor more reactions (e.g., a polymerization reaction, a decompositionreaction in which a precursor to a monomer decomposes to form a monomer,a decomposition reaction in which a precursor to an initiator decomposesto form an initiator) occurring in the reaction volume. The plasma maybe a phase of matter which comprises particles which are charged and/orwhich comprise a free radical.

In some embodiments, plasma is provided in the form of a wave, such as aradio frequency wave. The plasma may be provided at a frequency ofgreater than or equal to 3 MHz, greater than or equal to 5 MHz, greaterthan or equal to 7.5 MHz, greater than or equal to 10 MHz, greater thanor equal to 12.5 MHz, greater than or equal to 15 MHz, greater than orequal to 17.5 MHz, greater than or equal to 20 MHz, greater than orequal to 25 MHz, greater than or equal to 30 MHz, greater than or equalto 35 MHz, or greater than or equal to 40 MHz. In some embodiments, theplasma is provided at a frequency of less than or equal to 50 MHz, lessthan or equal to 35 MHz, less than or equal to 30 MHz, less than orequal to 25 MHz, less than or equal to 20 MHz, less than or equal to17.5 MHz, less than or equal to 15 MHz, less than or equal to 12.5 MHz,less than or equal to 10 MHz, less than or equal to 7.5 MHz, or lessthan or equal to 5 MHz. Combinations of the above-referenced ranges arealso possible (e.g., greater than or equal to 7.5 MHz and less than orequal to 20 MHz, greater than or equal to 10 MHz and less than or equalto 15 MHz, or greater than or equal to 10 MHz and less than or equal to20 MHz). Other ranges are also possible.

In some embodiments, the plasma is supplied in the form of one or morepulses. Pulses may occur at any frequency. In some embodiments, theplasma is supplied in the form of pulses with a frequency of greaterthan or equal to 0.25 kHz, greater than or equal to 0.5 kHz, greaterthan or equal to 0.75 kHz, greater than or equal to 1 kHz, greater thanor equal to 1.5 kHz, greater than or equal to 2 kHz, greater than orequal to 3 kHz, greater than or equal to 5 kHz, greater than or equal to7.5 kHz, greater than or equal to 10 kHz, greater than or equal to 15kHz, greater than or equal to 25 kHz, greater than or equal to 50 kHz,or greater than or equal to 75 kHz. In some embodiments, the plasma issupplied in the form of pulses with a frequency of less than or equal to100 kHz, less than or equal to 75 kHz, less than or equal to 50 kHz,less than or equal to 25 kHz, less than or equal to 15 kHz, less than orequal to 10 kHz, less than or equal to 7.5 kHz, less than or equal to 5kHz, less than or equal to 3 kHz, less than or equal to 2 kHz, less thanor equal to 1.5 kHz, less than or equal to 1 kHz, less than or equal to0.75 kHz, or less than or equal to 0.5 kHz. Combinations of theabove-referenced ranges are also possible (e.g., greater than or equalto 0.5 kHz and less than or equal to 10 kHz, greater than or equal to 1kHz and less than or equal to 15 kHz, or greater than or equal to 1 kHzand less than or equal to 10 kHz). Other ranges are also possible.

In some embodiments, the plasma is supplied in the form of pulses whichcomprise a duty cycle. They duty cycle is equivalent to the amount oftime for which the plasma is applied divided by the total cycle time(the sum of the time for which the plasma is applied and the time forwhich the plasma is not applied). Any suitable duty cycle may beemployed. In some embodiments, the plasma is supplied in the form ofpulses which comprise a duty cycle of greater than or equal to 0.02,greater than or equal to 0.05, greater than or equal to 0.1, greaterthan or equal to 0.2, greater than or equal to 0.3, greater than orequal to 0.4, or greater than or equal to 0.5. In some embodiments, theplasma is supplied in the form of pulses which comprise a duty cycle ofless than or equal to 0.75, less than or equal to 0.5, less than orequal to 0.4, less than or equal to 0.3, less than or equal to 0.2, lessthan or equal to 0.1, or less than or equal to 0.05. Combinations of theabove-referenced ranges are also possible (e.g., greater than or equalto 0.05 and less than or equal to 0.2). Other ranges are also possible.In some embodiments, the plasma is supplied to the reaction volume at aconstant intensity.

In some embodiments, the plasma is supplied in the form of a remoteplasma. A remote plasma may be supplied at any distance from thesubstrate. In some embodiments, the plasma is supplied at a distancefrom the substrate of greater than or equal to 1 cm, greater than orequal to 3 cm, greater than or equal to 5 cm, greater than or equal to 8cm, greater than or equal to 10 cm, greater than or equal to 15 cm,greater than or equal to 20 cm, greater than or equal to 25 cm, orgreater than or equal to 30 cm. In some embodiments, the plasma issupplied at a distance from the substrate of less than or equal to 50cm, less than or equal to 30 cm, less than or equal to 25 cm, less thanor equal to 20 cm, less than or equal to 15 cm, less than or equal to 10cm, less than or equal to 8 cm, less than or equal to 5 cm, or less thanor equal to 3 cm. Combinations of the above-referenced ranges are alsopossible (e.g., greater than or equal to 1 cm and less than or equal to30 cm, greater than or equal to 3 cm and less than or equal to 25 cm, orgreater than or equal to 8 cm and less than or equal to 50 cm). Otherranges are also possible.

The plasma may be provided at any suitable power density. The powerdensity of a plasma is equivalent to the energy provided by the plasmaper square centimeter plasma electrode. In some embodiments, the plasmais present at a power density of greater than or equal to 0.5 mW/cm²,greater than or equal to 0.75 mW/cm², greater than or equal to 0.1mW/cm², greater than or equal to 1.5 mW/cm², greater than or equal to 2mW/cm², greater than or equal to 5 mW/cm², greater than or equal to 7.5mW/cm², greater than or equal to 10 mW/cm², greater than or equal to12.5 mW/cm², greater than or equal to 15 mW/cm², greater than or equalto 20 mW/cm², greater than or equal to 30 mW/cm², greater than or equalto 35 mW/cm², greater than or equal to 40 mW/cm², or greater than orequal to 45 mW/cm². In some embodiments, the plasma is present at apower density of less than or equal to 50 mW/cm², less than or equal to45 mW/cm², less than or equal to 40 mW/cm², less than or equal to 35mW/cm², less than or equal to 30 mW/cm², less than or equal to 25mW/cm², less than or equal to 20 mW/cm², less than or equal to 15mW/cm², less than or equal to 12.5 mW/cm², less than or equal to 10mW/cm², less than or equal to 7.5 mW/cm², less than or equal to 5mW/cm², less than or equal to 2 mW/cm², less than or equal to 1.5mW/cm², less than or equal to 1 mW/cm², or less than or equal to 0.75mW/cm². Combinations of the above-referenced ranges are also possible(e.g., greater than or equal to 0.5 mW/cm² and less than or equal to 1mW/cm², greater than or equal to 0.5 mW/cm² and less than or equal to 2mW/cm², greater than or equal to 0.75 mW/cm² and less than or equal to 5mW/cm², greater than or equal to 1 mW/cm² and less than or equal to 10mW/cm², or greater than or equal to 0.5 mW/cm² and less than or equal to15 mW/cm²). Other ranges are also possible.

When present, the plasma may be substantially uniform throughout areaction volume to which it is supplied. Plasma uniformity may becharacterized by the ratio of the standard deviation of the powerdensity over the reaction volume to the average power density over thereaction volume. In some embodiments, the ratio of the standarddeviation of the power density over the reaction volume to the averagepower density over the reaction volume is less than or equal to 25%,less than or equal to 20%, less than or equal to 15%, less than or equalto 10%, or less than or equal to 5%. Other ranges are also possible.

In some embodiments, a high plasma uniformity is achieved byincorporating certain design elements into the reaction volume and/ordeposition chamber. For example, a reaction volume and/or depositionchamber may comprise an electrode and coupling near the center of theelectrode. As another example, a reaction volume and/or depositionchamber may comprise a shielded inlet power source. Other designfeatures which may improve plasma uniformity in a reaction volume mayalso be incorporated.

As described elsewhere herein, in some embodiments, a system comprisesone or more sources configured to introduce and/or remove one or morespecies from the reaction volume. The sources may be sources that are influidic communication with the reaction volume at all times, or may besources that may be placed in and/or removed from fluidic communicationwith the reaction volume (e.g., reversibly). Further detail regardingspecific types of sources are provided below.

The sources described herein may have a variety of suitable forms. Insome embodiments, a source takes the form of a reservoir of a material(or of vacuum) that may be placed in and/or removed from fluidiccommunication with the reaction volume by a port. As one example, asource of gas may take the form of and/or comprise a gas cylinder (e.g.,comprising the pressurized gas). The port may separate the reactionvolume from source, and may be opened and/or closed to place the sourcein and/or out of fluidic communication with the reaction volume. Theport may be in direct or indirect fluidic communication with the source.For instance, the port may be in fluidic communication with the sourcevia tubing.

The interface between a port and the reaction volume may have a varietyof suitable designs. In some embodiments, the port has a single openingthrough which, when the port is open, the source is placed in fluidiccommunication with the reaction volume. The single opening may have avariety of suitable shapes and sizes. For instance, it may be round,rectangular, square, etc. Some suitable ports have multiple openings. Asone specific example, a port may comprise a plurality of openings. Theplurality of openings may be positioned along a wall of the reactionvolume and/or along a tube present in the reaction volume.

In some embodiments, a system comprising two sources comprises ports influidic communication with the sources that are positioned opposite toeach other across the reaction volume. However, it is also possible fora system to, additionally or alternatively, comprise such ports that arenot positioned opposite to each other. Such ports may be positioned onopposing sides of a reaction volume but staggered such that they are notdirectly opposite each other or may be positioned on adjacent sides of areaction volume.

In some embodiments, in addition to or instead of a port, a flowcontroller may be positioned between a source and a reaction volume. Asone example, in some embodiments, a mass flow controller is placedbetween a source of gas and the reaction volume. As another example, andas described elsewhere herein, a throttling valve may be placed betweena source of vacuum and a reaction volume.

As also described elsewhere herein, in some embodiments, a source and/orplurality of sources is capable of and/or configured to introduce a gasand/or combination of gases that may react to deposit a fluorinatedpolymeric coating on a substrate. The gas and/or combination of gasesmay comprise a process gas. The process gas may comprise one or moregaseous monomers (e.g., one or more gaseous monomers that may undergo apolymerization reaction to form a fluorinated polymer, such as one ormore fluorinated monomers). In some embodiments, the process gascomprises one or more species that are not themselves monomers, butwhich may form monomers in the reaction volume (in other words, speciesthat are precursors to monomers). For instance, in some embodiments, aprocess gas comprises one or more species that are configured to undergoa chemical reaction to form a monomer inside the reaction volume, suchas a decomposition and/or pyrolization reaction. This chemical reactionmay be catalyzed by one or more conditions and/or species present in thereaction volume. For instance, the chemical reaction may be catalyzed byheat, such as by exposure to a heated filament. It is also possible fora process gas to comprise an initiator and/or a carrier gas (e.g., aninert gas, such as nitrogen, helium, and/or argon).

Non-limiting examples of suitable monomers and/or monomeric precursors(i.e., species that may undergo a reaction to form a monomer) includeC₃F₆O (HFPO or hexafluoropropylene oxide, which may be a species thatdecomposes to form a monomer, such as upon the application of heatthereto from a filament), C₂F₄, C₃F₈, CF₃H, CF₂H₂, CF₂N₂(difluordiaxirine), CF₃COCF₃, CF₂ClCOCF₂Cl, CF₂ClCOCFCl₂, CF₃COOH,difluorohalomethanes (e.g., CF₂Br, CF₂HBr, CF₂HCl, CF₂Cl₂ and CF₂FCl),difluorocyclopropanes (e.g., C₃F₆, C₃F₄H₂, C₃F₂Cl₄, C₂F₃Cl₃ andC₃F₄Cl₂), trifluoromethylfluorophosphanes (e.g., (CF₃)₃PF₃, (CF₃)₃PF₃,and (CF₃)PF₄), and trifluoromethylphosphino compounds (e.g., (CF₃)₃P,(CF₃)₂P—P(CF₃)₂, (CF₃)₂PX and CF₃PX₂, wherein X is F, Cl or H). It isalso possible for two or more of the above-described gases to beprovided in combination with each other (e.g., by a single source, bytwo or more sources).

In some embodiments, a process gas further comprises one or more carriergases and/or one or more carrier gases are provided by a source. Thecarrier gas(es) may serve to dissolve and/or assist with thetransportation of the monomers. Non-limiting examples of suitablecarrier gases include inert gases (e.g., nitrogen, helium, argon).

As described elsewhere herein, it is also possible for a system tocomprise a source of vacuum. The source of vacuum may be configured toevacuate the reaction volume when in fluidic communication therewith.This may be advantageous when, for instance, the reaction volumeinitially comprises a combination of gases that it would be undesirablefor the reaction volume to include during the deposition of afluorinated polymeric coating. For instance, and without wishing to bebound by any particular theory, it is believed that some gases mayinhibit polymerization reactions. Such gases may react with the growingpolymeric chains before they reach an appreciable length in a mannerthat terminates further growth and/or may react with monomers prior tobeing incorporated into growing polymeric chains in a manner thatrenders them non-reactive. Non-limiting examples of such gases includeair, water vapor, acetone, and isopropanol.

Another example of a situation in which it may be desirable to removeone or more gases from a reaction volume is at the conclusion of a stepperformed during the deposition of a coating. During deposition of thecoating, the reaction volume may comprise a variety of reactive and/ortoxic gases. It may be desirable for the reaction volume to be purged ofsuch gases before one or more further processes are performed. Forinstance, if the system is employed to perform a method comprisingsequentially depositing two layers with two distinct chemicalcompositions, it may be desirable to remove the gases that reacted toform the first layer prior to beginning deposition of the second layer.Removal of these species may facilitate the deposition of a second layerthat has the desired chemical composition, as it may prevent theincorporation of reaction products of these gases into the second layerand/or deleterious reactions between these gases and the gasesconfigured to react to form the second layer.

A third example of a situation in which it may be desirable to removeone or more gases from a reaction volume is at the conclusion of aprocess for depositing a coating. As described above, the reactionvolume may comprise reactive and/or toxic gases during coatingdeposition. It may be undesirable for an operator to be exposed to suchgases and/or for such gases to be released in an uncontrolled manner toan environment external to the reaction volume. Accordingly, in suchcases, it may be desirable for the gases present in the reaction volumeto be removed therefrom prior to exposure of the reaction volume to anenvironment external thereto to retrieve a coated substrate at theconclusion of a coating process.

A variety of suitable types of sources of vacuum may be employed. As anexample, in some embodiments, a source of vacuum comprises a vacuumpump. The vacuum pump, when turned on and in fluidic communication withthe reaction volume, may evacuate the reaction volume by pumping out itscontents.

In some embodiments, a source of vacuum has one or more properties thatrender it advantageous for removing air and/or other gases from areaction volume. As one example, in some embodiments, a source of vacuumis configured such that the removal of gas from the reaction volumeoccurs over a period of time that is relatively slow. Without wishing tobe bound by any particular theory, it is believed that relatively slowremoval of gas from a reaction volume may be desirable when small and/orlightweight parts are positioned inside the reaction volume. Such partsare believed to have a tendency to be moved by currents of gas that maybe generated when gas rapidly flows out of the reaction volume uponexposure to a source of vacuum. It is believed that slower removal ofgas from the reaction volume may reduce the magnitude and/or number ofsuch currents.

The slow and/or controlled removal of gas from a reaction volume may beaccomplished by the use of a throttling valve positioned between thesource of vacuum and the reaction chamber. The throttling valve mayrestrict the exposure of the reaction volume to the source of vacuumand/or may slowly open to allow increasing exposure of the reactionvolume to the source of vacuum over time. These processes may cause thesource of vacuum to remove the gases therein at a slower rate than thesource of vacuum would absent such a throttling valve.

In some embodiments, a system is configured such that one or more gasesmay be removed from a reaction volume in a manner other than placing asource of vacuum in fluidic communication with the reaction volume. Asone example, in some embodiments, a system may be configured such thatone or more gases may be introduced into the reaction volume thatdisplace other gases present in the reaction volume therefrom. Forinstance, a system may be configured such that an inert gas (and/or aplurality of inert gases) may be introduced into a reaction volume todisplace a reactive and/or toxic gas (and/or a plurality of reactiveand/or toxic gases). The inert gas(es) may be introduced from one ormore sources in fluidic communication with the reaction volume, such asone or more sources other than the source(s) supplying (and/orpreviously supplying) the reactive and/or toxic gas(es).

Introducing one or more inert gases into a reaction volume may beperformed instead of removing gas(es) from the reaction volume byplacing a source of vacuum in fluidic communication therewith, or inconjunction with such a process. In the latter case, the source ofvacuum, when in fluidic communication with the reaction volume, mayevacuate both the inert gas(es) and the reactive and/or toxic gas(es)from the reaction volume. In one specific example, the source of vacuummay be placed in fluidic communication with a reaction volume thatcomprises the reactive and/or toxic gases and that is in fluidiccommunication with one or more sources of inert gases. The source ofvacuum may initially evacuate both types of gases. Then, the source(s)of inert gases may be removed from fluidic communication with thereaction volume while maintaining fluidic communication between thesource of vacuum and the reaction volume. The source of vacuum may thenfurther evacuate the reaction volume of any remaining gases therein.

In some embodiments, a system comprises an outlet that may be placed influidic communication with a reaction volume. The outlet may beconfigured to allow one or more gases present in the reaction volume toflow out of the reaction volume when in fluidic communication with thereaction volume. The outlet may be in fluidic communication with alocation to which the gases present in the reaction volume may be safelyexhausted, such as a fume hood. In some embodiments, the outlet may bein reversible fluidic communication with the reaction volume. Forinstance, the outlet may be removed from fluidic communication with thereaction volume during time periods in which the reaction volume is influidic communication with a source vacuum. It is also possible for theoutlet to be configured such that gases may flow out of the reactionvolume through the outlet but that gases are not able to flow into thereaction volume through the outlet. For instance, in some embodiments,the outlet may comprise a check valve, a gas bubbler, and/or anothercomponent that provides this functionality. In some embodiments, theoutlet is configured to allow for gases to both flow into and flow outof the reaction volume, but the gases flowing into the reaction volume(e.g., from one or more sources) may be flowing into the reaction volumein sufficient amounts and/or at sufficient rates such that there is noappreciable flow into the reaction volume from the outlet.

In some embodiments, a system described herein comprises a coolingsystem. The cooling system may be configured to cool one or moreportions of the reaction volume. For instance, as an example, in someembodiments, a system comprises a cooling system configured to cool asubstrate being coated in the reaction volume. Advantageously, coolingthe substrate may promote the formation of a coating thereon having adesired morphology, having a desired molecular weight, and/or that formsat a desired rate. By way of example, the temperature of the substratemay affect the tendency of gaseous species (e.g., gaseous polymers) todeposit on the substrate. For instance, if the substrate is cooler thanone or more other portions of the reaction volume, the gaseous speciesmay deposit preferentially on the substrate in comparison to other,warmer surfaces in the reaction volume. As another example, thetemperature of the substrate may affect the mobility of any speciesdeposited thereon. Without wishing to be bound by any particular theory,it is believed that heat enhances the mobility of species on a surface,and so cooler substrates may suppress the mobility of any speciesdeposited thereon in comparison to warmer substrates. It is alsobelieved that cooled substrates may exhibit reduced rates ofpolymerization thereon than in the comparatively warmer gaseousatmosphere in the reaction volume.

In some embodiments, a cooled substrate may facilitate the deposition ofcoatings onto substrates that would otherwise undergo one or moreundesirable processes during the deposition process. For instance, insome embodiments, it may be desirable to deposit a coating onto asubstrate that would otherwise melt and/or undergo a deleteriouschemical reaction (e.g., a decomposition reaction, a reaction with oneor more gases present in the reaction volume) during coating. Coolingthe substrate may reduce and/or eliminate the tendency of the substrateto undergo such processes.

When present, cooling systems may have a variety of designs. In someembodiments, a cooling system comprises a cooling element. The coolingelement may be a component of the cooling system that is configured tobe held at a temperature cooler than one or more other components of thereaction volume. The cooling element may be configured to be maintainedat a constant temperature (e.g., at a set point), within a constanttemperature range (e.g., in a defined range around a set point), and/orwithin a variable temperature range (e.g., at any temperature below acertain value, at the coolest temperature at which it can be cooled to).The cooling element may be an article that is configured to cool asubstrate. As an example, the cooling element may be configured to coola substrate by being cooled itself. It may further directly contact oneor more portions of the substrate, directly contact one or morecomponents of the reaction volume positioned directly adjacent to one ormore portions of the substrate (e.g., a thermally conductive layerpositioned directly between the cooling element and one or more portionsof the substrate), and/or be in close proximity to the substrate suchthat it cools a gas in close proximity to the substrate that then coolsthe substrate.

In some embodiments, a cooling element comprises one or more materialswith a relatively high thermal conductivity. As an example, in someembodiments, a cooling element comprises a metal (e.g., aluminum).

A cooling element may, itself, be cooled by one or more furthercomponents of the cooling system. As an example, in some embodiments, acooling system further comprises one or more components configured tocool the cooling element. One example of a suitable such component is asystem configured to circulate a cooled fluid across and/or through thecooling element (e.g., across a surface of the cooling element otherthan a surface contacting the substrate, through the body of the coolingelement). When the cooling element is configured such that a fluid maybe circulated through and/or across the cooling element, the coolingelement may be connected to a source and/or a drain for such fluid. Insome embodiments, this connection and/or disconnection is reversibleand/or may be performed relatively easily. This may advantageouslyfacilitate easy introduction and/or removal of the cooling element. Forinstance, in some embodiments, a cooling element is connected to asource and/or drain for a fluid by quick-connects. Another example of afurther component of a cooling system is a component configured to coola coolant, such as a chiller. A third example is a component configuredto cool the cooling element is a combination of electronic componentsthat cools the cooling element by Peltier cooling.

In some embodiments, a cooling element is positioned in the reactionvolume in a manner that promotes the cooling of the substrate in anadvantageous manner. As one example, in some embodiments, a coolingelement is positioned around the substrate. FIG. 8 shows onenon-limiting embodiment of a top view of a cooling element having thisproperty. In FIG. 8, the cooling element 1414 is positioned around thesubstrate 1514. The cooling element 1414 shown in FIG. 8 surrounds thesubstrate 1514 laterally on all sides.

Like the embodiment shown in FIG. 8, it is possible for a coolingelement to be positioned around a substrate but have a different shapethan the substrate and/or not contact the substrate. It is also possiblefor a cooling element to be positioned around a substrate but havesubstantially the same cross-sectional shape as the substrate and/or tocontact the substrate in one or more locations (e.g., in one or morediscrete locations, along the entirety of the external surface of thesubstrate, along the entirety of the external surface of the substratethat is positioned below a certain height). In some embodiments, acooling element is positioned completely around the substrate (i.e.,such that it surrounds the substrate laterally on all sides). It is alsopossible for a cooling element to be positioned partially around thesubstrate. Such cooling elements may be positioned proximate some, butnot all, of the lateral sides of the substrate. For instance, asubstrate may have a square cross-section and a cooling element maypositioned proximate three of its four lateral sides.

Similarly, like the embodiment shown in FIG. 8, it is possible for acooling element to be positioned around a substrate but not positionedbeneath or above the substrate. It is also possible for a coolingelement to be positioned both around the substrate and beneath thesubstrate and/or both around the substrate and above the substrate. Insuch cases, the cooling element may be positioned beneath and/or aboveall portions of the substrate. It is also possible for the coolingelement to be positioned beneath and/or above one or more portions ofthe substrate but not beneath and/or above one or more other portion(s)of the substrate. The portion(s) of the cooling element positionedbeneath and/or above the substrate may exclusively comprise portionsthat directly contact the substrate, may comprise one or more portionsthat directly contact the substrate and one or more portions that do notdirectly contact the substrate, and/or may lack any portions thatdirectly contact the substrate.

In some embodiments, a cooling element and a substrate may be positionedsuch that one is freely movable with respect to the other. By way ofexample, in some embodiments, a cooling element and a substrate arepositioned such that the substrate is freely-movable with respect to thecooling element. As another example, in some embodiments, a coolingelement and a substrate are positioned such that the cooling element isfreely-movable with respect to the substrate. In some such embodiments,the cooling element and/or the substrate are not in direct contact witheach other. Regardless of whether or not the cooling element and thesubstrate comprise portions that are in direct contact with each other,the substrate may be freely moveable with respect to the cooling elementif it can be moved in at least one direction for an appreciable distance(e.g., at least 0.1 inch, at least 0.25 inches, at least 0.5 inches,and/or at least 1 inch) while maintaining the cooling element in aconstant position. The direction may be vertical, may be horizontal, maybe in a direction towards one or more portions of the cooling element,and/or may be in a direction away from one or more portions of thecooling element. In some embodiments, the substrate may be capable ofbeing moved with respect to the cooling element in all directions for anappreciable distance.

Similarly, the cooling element may be freely movable with respect to thesubstrate if it can be moved in at least one direction for anappreciable distance (e.g., at least 0.1 inch, at least 0.25 inches, atleast 0.5 inches, and/or at least 1 inch) while maintaining thesubstrate in a constant position. Likewise, the direction may bevertical, may be horizontal, may be in a direction towards one or moreportions of the substrate, and/or may be in a direction away from one ormore portions of the substrate. In some embodiments, the cooling elementmay be capable of being moved with respect to the substrate in alldirections for an appreciable distance.

In some embodiments, a cooling element has a design such that it has oneor more dimensions having a desirable size. For instance, in someembodiments, a cooling element has a height such that the coolingelement extends from the bottom of a substrate around which it ispositioned to the top (or beyond the top) of the substrate around whichit is positioned. Without wishing to be bound by any particular theory,it is believed that cooling elements having this property mayadvantageously be capable of cooling a substrate uniformly. Substratesthat are relatively tall may, in the absence of a cooling element withsuch a design, experience a temperature gradient from upper, uncooledportions to lower, cooled portions. This temperature gradient maydisadvantageously cause a fluorinated polymeric coating to deposit onthe substrate in an uneven manner, as it is believed that thetemperature of the substrate affects the physical properties of thecoating formed thereon. It is also possible for tall substrates to beinsufficiently cooled by cooling elements that do not extendsufficiently high on the substrate to fail to appropriately cool theupper portions of the substrate, which may cause the upper portions ofthe substrate to undergo the undesirable processes due to overheatingdescribed elsewhere herein.

In some embodiments, a cooling element does not extend to the fullheight of the substrate, but extends to a height that is taller than oneor more features of the substrate. As one example, in some embodiments,a substrate comprises one or more depressions in its surface, and thecooling element may have a height that is taller than the upper surfaceof the depressions. FIG. 9 shows one example of a cooling element havingthis property. In FIG. 9, which depicts a cross-section of the coolingelement and the substrate, the cooling element 1416 is positioned aroundand beneath the substrate 1516, which further comprises two depressions1616 and 1666. As shown in FIG. 9, the cooling element 1416 extends to aheight that is taller than the upper surface of the lower depression1616 but does not extend to a height that is taller than the top of thesubstrate. The surfaces of depressions in a substrate are closer to thebase of the substrate than the upper surfaces of the substrate. For thisreason, it is believed that, if cooling is only provided from the baseof the substrate, the surfaces of the depressions may be cooled to alower temperature than the upper surfaces of the substrate, which, forthe reasons described elsewhere herein, may cause the fluorinatedpolymeric coating to deposit onto the substrate in a non-uniform manner.

In some embodiments, a cooling element has a height of greater than orequal to 0.1 inch, greater than or equal to 0.15 inches, greater than orequal to 0.2 inches, greater than or equal to 0.25 inches, greater thanor equal to 0.3 inches, greater than or equal to 0.4 inches, greaterthan or equal to 0.5 inches, greater than or equal to 0.75 inches,greater than or equal to 1 inch, greater than or equal to 1.5 inches,greater than or equal to 2 inches, greater than or equal to 3 inches,greater than or equal to 4 inches, greater than or equal to 5 inches,greater than or equal to 7.5 inches, greater than or equal to 10 inches,greater than or equal to 12.5 inches, greater than or equal to 15inches, greater than or equal to 17.5 inches, or greater than or equalto 20 inches. In some embodiments, a cooling element has a height ofless than or equal to 24 inches, less than or equal to 20 inches, lessthan or equal to 17.5 inches, less than or equal to 15 inches, less thanor equal to 12.5 inches, less than or equal to 10 inches, less than orequal to 7.5 inches, less than or equal to 5 inches, less than or equalto 4 inches, less than or equal to 3 inches, less than or equal to 2inches, less than or equal to 1.5 inches, less than or equal to 1 inch,less than or equal to 0.75 inches, less than or equal to 0.5 inches,less than or equal to 0.4 inches, less than or equal to 0.3 inches, lessthan or equal to 0.25 inches, less than or equal to 0.2 inches, or lessthan or equal to 0.15 inches. Combinations of the above-referencedranges are also possible (e.g., greater than or equal to 0.1 inch andless than or equal to 24 inches, or greater than or equal to 0.5 inchesand less than or equal to 5 inches). Other ranges are also possible.

When present, a cooling element may be configured to be maintained atand/or maintain a substrate at a variety of suitable temperatures. Insome embodiments, a cooling element is configured to be maintained atand/or to maintain a substrate at a temperature of greater than or equalto 0° C., greater than or equal to 1° C., greater than or equal to 2°C., greater than or equal to 3° C., greater than or equal to 5° C.,greater than or equal to 7.5° C., greater than or equal to 10° C.,greater than or equal to 15° C., greater than or equal to 20° C.,greater than or equal to 25° C., greater than or equal to 30° C.,greater than or equal to 40° C., greater than or equal to 50° C.,greater than or equal to 75° C., greater than or equal to 100° C., orgreater than or equal to 125° C. In some embodiments, a cooling elementis configured to be maintained at and/or to maintain a substrate at atemperature of less than or equal to 150° C., less than or equal to 125°C., less than or equal to 100° C., less than or equal to 75° C., lessthan or equal to 50° C., less than or equal to 40° C., less than orequal to 30° C., less than or equal to 25° C., less than or equal to 20°C., less than or equal to 15° C., less than or equal to 10° C., lessthan or equal to 7.5° C., less than or equal to 5° C., less than orequal to 3° C., less than or equal to 2° C., or less than or equal to 1°C. Combinations of the above-referenced ranges are also possible (e.g.,greater than or equal to 0° C. and less than or equal to 150° C.,greater than or equal to 0° C. and less than or equal to 100° C., orgreater than or equal to 5° C. and less than or equal to 100° C.). Otherranges are also possible.

The ranges in the preceding paragraph may independently refer to theaverage temperature on an external surface of the cooling element (e.g.,a surface closest to the substrate) and/or to the average temperature ofan external surface of a substrate (e.g., a surface closest to thecooling element, a surface opposite the cooling element, an uppersurface).

As described elsewhere herein, in some embodiments, a reaction volumecomprises one or more gases. The reaction volume may comprise such gasesin advantageous amounts and/or that have one or more other advantageousproperties. Further information regarding such properties is providedbelow.

One example of an advantageous property that gases in a reaction volumemay have is flowing through the reaction volume in a one-dimensionalmanner. One-dimensional flow may be flow in which the relevant gasesflow primarily or entirely in one direction. It is also possible forone-dimensional flow to be laminar. As one example of one-dimensionalflow, the one-dimensional flow of a gas may be flow in which the gasflows entirely in one direction and does not flow in any direction otherthan that direction. As another example, in some embodiments,one-dimensional flow of a gas comprises flow that is primarily, but notentirely in one direction. For instance, the one-dimensional flow maycomprise small amounts of flow in directions other than the primarydirection. These small amounts of flow may make up less than or equal to50%, less than or equal to 20%, less than or equal to 10%, and/or lessthan or equal to 5% of the one-dimensional flow.

When two or more different types of gases are flowing through a reactionvolume (e.g., two or more types of gases provided from a common source,two or more types of gases provided from different sources, providedfrom the same source), the different types of gases may together exhibitone-dimensional flow in a single direction. In other words, all of thegases together may flow entirely in the same direction and/or maytogether comprise amounts of flow in a direction other than the primarydirection in one or more of the ranges described in the precedingparagraph. It is also possible for two or more different types of gases(e.g., provided from different sources, provided from the same source)to have flows that differ from each other. For instance, two or moredifferent types of gases may each flow through the reaction volume in aone-dimensional manner, but the directions in which the different typesof gases flow may differ from each other. As another example, in someembodiments, one or more types of gases may exhibit one-dimensional flowand one or more types of gases may not exhibit one-dimensional flow(e.g., one or more types of gases may exhibit convective and/orturbulent flow).

When one-dimensional flow is present in a reaction volume, the directionof the one-dimensional flow may generally be selected as desired. Insome embodiments, the direction of the one-dimensional flow may be adirection that extends from a location at which a gas is introduced intothe reaction volume to an outlet of the reaction volume. For instance,in some embodiments, the direction of one-dimensional flow is adirection that extends from a port in fluidic communication with asource of the relevant gas to an outlet. As another example, in someembodiments, the direction of one-dimensional flow is from one wallenclosing the reaction volume to another, opposite wall enclosing thereaction chamber. As a third example, in some embodiments, the directionof one dimensional-flow is parallel to the direction in which a filamentand/or a plurality of filaments extends across the reaction volume(e.g., parallel to the longest dimension of a wire extending across thereaction volume). It is also possible for the direction ofone-dimensional flow to be perpendicular to the direction in which afilament and/or a plurality of filaments extends across the reactionvolume and/or to be at any angle in between parallel and perpendicularto the direction in which a filament and/or plurality of filamentsextends across the reaction volume.

When a reaction volume comprises one-dimensional flow, theone-dimensional flow may be present in all of the reaction volume or maybe present in some portions of the reaction volume but not others. Theportion(s) of the reaction volume in which the one-dimensional flow isabsent may lack flow (e.g., the gas in these portion(s) of the reactionvolume may be stationary and/or substantially stationary) or maycomprise flow that is not one-dimensional (e.g., flow in a differentdirection, flow in a plurality of different directions). In someembodiments, portion(s) of the reaction volume proximate a port influidic communication with a source of gases exhibit one-dimensionalflow. As one example, in some embodiments, one or more such ports may bepositioned proximate an upper portion of the reaction volume and theupper portion of the reaction volume may display one-dimensional flow.

In some embodiments, one-dimensional flow occurs across at least the top25% of the reaction volume, at least the top 50% of the reaction volume,at least the top 67% of the reaction volume, at least the top 75% of thereaction volume, at least the top 80% of the reaction volume, and/or atleast the top 90% of the reaction volume. In some embodiments,one-dimensional flow occurs across no more than the top 95% of thereaction volume, no more than the top 90% of the reaction volume, nomore than the top 80% of the reaction volume, no more than the top 75%of the reaction volume, no more than the top 67% of the reaction volume,or no more than the top 50% of the reaction volume. Combinations of theabove-referenced ranges are also possible (e.g., at least the top 25%and no more than the top 95% of the reaction volume). Other ranges arealso possible.

A reaction volume may be configured to allow one-dimensional flowtherethrough in a variety of suitable manners. As one example, in someembodiments, one-dimensional flow is obtained by orienting a port influidic communication with a source of gas such that the port directsthe gas to a wall of the reaction volume positioned proximate the port.It is believed that this design may cause the gas to initially flowoutwards in all directions from the port, but then rebound from the walland flow in substantially one direction (i.e., perpendicular to thewall) after doing so. FIG. 10 shows one non-limiting embodiment of aport positioned in this manner. In FIG. 10, the port 1718 is positionedproximate the wall 1078 of the reaction volume 318. Gas is believed toflow out of the port 1718 in the manner shown by the arrows.

Another example of a manner in which one-dimensional flow may beobtained is by use of a plurality of baffles. The baffles may direct thegas to flow in a one-dimensional manner.

In some embodiments, a reaction volume has a relatively low pressure atone or more points in time. This relatively low pressure may be presentat times when, for instance, a reaction (e.g., a reaction to deposit afluorinated polymeric coating) is performed in the reaction volume. Insome embodiments, the pressure in the reaction volume is less than orequal to 100 Torr, less than or equal to 75 Torr, less than or equal to50 Torr, less than or equal to 20 Torr, less than or equal to 10 Torr,less than or equal to 7.5 Torr, less than or equal to 5 Torr, less thanor equal to 2 Torr, less than or equal to 1 Torr, less than or equal to750 mTorr, less than or equal to 500 mTorr, less than or equal to 200mTorr, less than or equal to 100 mTorr, less than or equal to 75 mTorr,less than or equal to 50 mTorr, less than or equal to 30 mTorr, lessthan or equal to 20 mTorr, less than or equal to 10 mTorr, less than orequal to 7.5 mTorr, less than or equal to 5 mTorr, or less than or equalto 2 mTorr. In some embodiments, the pressure in the reaction volume isgreater than or equal to 1 mTorr, greater than or equal to 2 mTorr,greater than or equal to 5 mTorr, greater than or equal to 10 mTorr,greater than or equal to 20 mTorr, greater than or equal to 30 mTorr,greater than or equal to 50 mTorr, greater than or equal to 75 mTorr,greater than or equal to 100 mTorr, greater than or equal to 200 mTorr,greater than or equal to 500 mTorr, greater than or equal to 750 mTorr,greater than or equal to 1 Torr, greater than or equal to 2 Torr,greater than or equal to 5 Torr, greater than or equal to 7.5 Torr,greater than or equal to 10 Torr, greater than or equal to 20 Torr,greater than or equal to 50 Torr, or greater than or equal to 75 Torr.Combinations of the above-referenced ranges are also possible (e.g.,less than or equal to 100 Torr and greater than or equal to 1 mTorr, orless than or equal to 10 Torr and greater than or equal to 5 mTorr).Other ranges are also possible.

In some embodiments, as described above, a reaction volume includes arelatively low level of air at one or more points in time. Thisrelatively low level of air may be present at times when, for instance,a reaction (e.g., a reaction to deposit a fluorinated polymeric coating)is performed in the reaction volume. In some embodiments, the amount ofair in the reaction volume may be in one or more of the ranges describedin the preceding paragraph with respect to the total pressure in thereaction volume (e.g., less than or equal to 30 mTorr, less than orequal to 20 mTorr, and/or less than or equal to 10 mTorr).

It is also possible for a reaction volume to include a relatively lowlevel of water. This relatively low level of water may be present attimes when, for instance, a reaction (e.g., a reaction to deposit afluorinated polymeric coating) is performed in the reaction volume. Insome embodiments, the amount of water in the reaction volume may be inone or more of the ranges described in the preceding paragraph withrespect to the total pressure in the reaction volume (e.g., less than orequal to 30 mTorr, less than or equal to 20 mTorr, and/or less than orequal to 10 mTorr).

It is also possible for a relatively low level of water in the reactionvolume to be evidenced by a relatively low level of relative humidity.The relative humidity of the reaction volume may be less than or equalto 0.5%, less than or equal to 0.4%, less than or equal to 0.3%, lessthan or equal to 0.2%, or less than or equal to 0.1%. The relativehumidity of the reaction volume may be greater than or equal to 0%,greater than or equal to 0.1%, greater than or equal to 0.2%, greaterthan or equal to 0.3%, or greater than or equal to 0.4%. Combinations ofthe above-referenced ranges are also possible (e.g., less than or equalto 0.5% and greater than or equal to 0%). Other ranges are alsopossible.

In some embodiments (e.g., during the deposition of a fluorinatedpolymeric coating therein), a reaction volume may comprise a relativelyhigh amount of monomers and/or of precursors to monomers. In someembodiments, monomers and/or precursors to monomers make up greater thanor equal to 1 mol %, greater than or equal to 2 mol %, greater than orequal to 5 mol %, greater than or equal to 7.5 mol %, greater than orequal to 10 mol %, greater than or equal to 15 mol %, greater than orequal to 20 mol %, greater than or equal to 30 mol %, greater than orequal to 40 mol %, greater than or equal to 50 mol %, or greater than orequal to 75 mol % of the gases in the reaction volume. In someembodiments, monomers and/or precursors to monomers make up less than orequal to 100 mol %, less than or equal to 75 mol %, less than or equalto 50 mol %, less than or equal to 40 mol %, less than or equal to 30mol %, less than or equal to 20 mol %, less than or equal to 15 mol %,less than or equal to 10 mol %, less than or equal to 7.5 mol %, lessthan or equal to 5 mol %, or less than or equal to 2 mol % of the gasesin the reaction volume. Combinations of the above-referenced ranges arealso possible (e.g., greater than or equal to 1 mol % and less than orequal to 100 mol %). Other ranges are also possible.

It should be understood that the ranges in the preceding paragraph mayindependently refer to the amounts of any of the following in thereaction volume: one type of monomer (e.g., in the presence of othertypes of monomers and/or a precursor to that monomer, in the absence ofeither or both of such species), all of the monomers together (e.g., inthe presence of precursors to one or more of the monomers, in theabsence of such species), one type of monomer and its precursor(s)(e.g., in the presence of other types of monomers and/or precursors toother types of monomers, in the absence of either or both of suchspecies), and all of the monomers and all of the precursors to monomerstogether.

As described elsewhere herein, in some embodiments, the systemsdescribed herein are suitable for and/or are employed for creatingfluorinated polymeric coatings on substrates. The fluorinated polymericcoatings may be formed by polymerizing gaseous monomers. Further detailsof this process are provided below.

One or more reactions may take place in the reaction volume to form thefluorinated polymeric coating. As described elsewhere herein, in someembodiments, one such reaction is a polymerization reaction. Thepolymerization reaction may proceed through a variety of suitablemechanisms. One example of such a mechanism is a chain growth reaction.Another example of such a mechanism is a step group reactions. In chaingrowth reactions and step growth reactions, a growing polymeric chaincomprises one or more reactive species at one or more of its ends. Thesereactive species may react with monomers, which may then be incorporatedinto the growing chain and themselves become reactive end groups thatmay react with further monomers.

In chain growth reactions, the monomers reacting to form the growingpolymeric chain may not themselves be reactive with other monomers untilactivated in some manner (e.g. by being incorporated into the growingpolymeric chain and/or by reacting with a species rendering themreactive, such as an initiator). Chain growth may accordingly proceed bygrowing individual polymeric chains by adding monomers until thereactive end groups are rendered unreactive. This may occur by reactionwith another reactive chain (thereby rendering both chains inactive) orwith another species that serves to inactivate the end group (e.g., acontaminant, such as oxygen). During the growth of any single chain, newchains may be forming and/or growing and/or the growth of other chainsmay be terminated. The reactive end groups may be reactive in a varietyof ways. As one example, in some embodiments, the reactive end groupscomprise free radicals. These free radicals may react with furthermonomers, and may pass the free radical to the monomers with which theyreact so that, after the reaction, the end group initially comprisingthe free radical is rendered unreactive and the newly-added monomerbecomes a reactive end group comprising the free radical.

Chain growth reactions may be reactions that begin spontaneously or maybe reactions that do not begin spontaneously. Chain growth reactionsthat occur spontaneously may be reactions in which the monomerspontaneously becomes reactive. As an example, some monomers decomposeto and/or undergo a reaction to form a species comprising a reactivespecies (e.g., a free radical) under the conditions present in areaction chamber. Chain grown reactions may occur non-spontaneously ifone or more of the reactants is provided in precursor form. Forinstance, in some embodiments, a chain growth reaction may not occuruntil the decomposition of a precursor to a monomer into the resultantmonomer. This decomposition process may be non-spontaneous (e.g., it mayrequire the application of heat, such as heat provided by a heatedfilament). After decomposition of the precursor to the monomer into themonomer, the resultant monomer may polymerize spontaneously.

It is also possible for a chain growth reaction to require and/or beaccelerated by an initiator. An initiator may be a species that readilyundergoes a reaction and/or decomposes to form a reactive species (e.g.,a species comprising a free radical). The initiator may undergo such areaction and/or decomposition more readily than any monomer(s) and/orother species also present in the reaction volume. After undergoing thereaction and/or decomposition, the initiator may react with monomers inthe same manner described above. Non-limiting examples of suitableinitiators include initiators comprising peroxide groups, persulfategroups, and/or azo groups. In some embodiments, an initiator comprisesone or more of tert-butyl peroxide and tert-amyl peroxide.

In step growth reactions, the monomers are typically reactive with eachother without activation. Step growth reactions may proceed by addingmonomers to growing chains, by joining growing chains together, and/orby forming new growing chains by reactions of monomers with each other.None of these processes typically inactivate the growing chains. Thereactive end groups and/or monomers may be reactive in a variety ofways. As one example, in some embodiments, the reactive end groups of agrowing chain comprise functional groups that are reactive with eachother. These functional groups may react with each other to formcovalent bonds that become the resultant polymeric chain's backbone.Step growth polymerization typically begins spontaneously, but may beaccelerated by the presence of heat and/or any species and/or reactioncondition that promotes the reactions between the monomers. It is alsopossible for a step growth polymerization reaction to not occurspontaneously. As one example, it is possible for a step growth reactionto occur between monomers whose precursors are provided to the reactionvolume. In this case, the step growth reaction may not occur until theprecursors are decomposed to form the monomers, which may only occurupon the application of energy (e.g., heat provided by a filament).

In some embodiments, one or more reactions other than polymerizationreactions may be performed in the reaction volume. As one example, insome embodiments, one or more decomposition reactions are performed inthe reaction volume. For instance, a species may be introduced into thereaction volume that is not itself a monomer, but may undergo adecomposition reaction to form a monomer. In some embodiments, thedecomposition of a species may be facilitated by one or more conditionspresent in the reaction volume. As an example, in some embodiments, thepresence of heat (e.g., from a heated filament) promotes thedecomposition of a precursor into a monomer.

As described elsewhere herein, in some embodiments, a polymerizationreaction occurs in the gas phase. The polymerization reaction may resultin the formation of a solid, polymeric particle surrounded by gas. Insome embodiments, a relatively high percentage of the totalpolymerization occurring in the reaction volume may be nucleated in thegas phase and/or may result in the production of polymeric particlessurrounded by gas. As an example, in some embodiments, greater than orequal to 50%, greater than or equal to 60%, greater than or equal to80%, greater than or equal to 90%, greater than or equal to 92.5%,greater than or equal to 95%, greater than or equal to 97.5%, greaterthan or equal to 99%, greater than or equal to 99.5%, or greater than orequal to 99.9% of the total polymerization occurring in the reactionvolume is nucleated in the gas phase and/or results in the production ofpolymeric particles surrounded by gas. In some embodiments, less than orequal to 100%, less than or equal to 99.9%, less than or equal to 99.5%,less than or equal to 99%, less than or equal to 97.5%, less than orequal to 95%, less than or equal to 92.5%, less than or equal to 90%,less than or equal to 80%, or less than or equal to 60% of the totalpolymerization occurring in the reaction volume is nucleated in the gasphase and/or results in the production of polymeric particles surroundedby gas. Combinations of the above-referenced ranges are also possible(e.g., greater than or equal to 50% and less than or equal to 100%, orgreater than or equal to 90% and less than or equal to 100%). Otherranges are also possible.

When present, particles formed by polymerization in the gas phase mayhave a variety of suitable sizes. In some embodiments, an averagediameter of the particles formed in the gas phase is greater than orequal to 0.5 nm, greater than or equal to 0.75 nm, greater than or equalto 1 nm, greater than or equal to 1.5 nm, greater than or equal to 2 nm,greater than or equal to 5 nm, greater than or equal to 10 nm, greaterthan or equal to 20 nm, greater than or equal to 50 nm, greater than orequal to 75 nm, greater than or equal to 100 nm, greater than or equalto 200 nm, greater than or equal to 500 nm, greater than or equal to 750nm, greater than or equal to 1 micron, greater than or equal to 2microns, greater than or equal to 5 microns, greater than or equal to7.5 microns, greater than or equal to 10 microns, or greater than orequal to 20 microns. In some embodiments, an average diameter of theparticles formed in the gas phase is less than or equal to 50 microns,less than or equal to 20 microns, less than or equal to 10 microns, lessthan or equal to 7.5 microns, less than or equal to 5 microns, less thanor equal to 2 microns, less than or equal to 1 micron, less than orequal to 750 nm, less than or equal to 500 nm, less than or equal to 200nm, less than or equal to 100 nm, less than or equal to 75 nm, less thanor equal to 50 nm, less than or equal to 20 nm, less than or equal to 10nm, less than or equal to 5 nm, less than or equal to 2 nm, less than orequal to 1.5 nm, less than or equal to 1 nm, or less than or equal to0.75 nm. Combinations of the above-referenced ranges are also possible(e.g., greater than or equal to 0.5 nm and less than or equal to 50microns, or greater than or equal to 1 nm and less than or equal to 1micron). Other ranges are also possible.

As also described elsewhere herein, the above-described polymerizationreactions may be employed to form a fluorinated polymer, such as afluorinated polymer that forms when surrounded by a gas and/or depositsto form a coating on a substrate. One example of a suitable fluorinatedpolymer is poly(tetrafluoroethylene). Another example of a suitablefluorinated polymer is a polymer comprising fluorine functional groups.

The level of fluorination in such polymers may be quantified by the CF₂fraction, which is equivalent to the fraction of repeat units in thepolymer that are CF₂ groups. In some embodiments, a reaction describedherein may result in the formation of a polymer that has a relativelyhigh CF₂ fraction. As an example, the CF₂ fraction may be greater thanor equal to 50%, greater than or equal to 75%, greater than or equal to90%, and/or greater than or equal to 95%. In some embodiments, the CF₂fraction is less than 100%, less than or equal to 95%, less than orequal to 90%, or less than or equal to 75%. Combinations of theabove-referenced ranges are also possible (e.g., greater than or equalto 75% and less than 100%). Other ranges are also possible. The CF₂fraction of a polymer may be determined by XPS.

Another way that the level of fluorination in a polymer may bequantified is by the atomic ratio of fluorine to carbon therein. In someembodiments, a polymer has an atomic ratio of fluorine to carbon ofgreater than or equal to 1.1, greater than or equal to 1.2, greater thanor equal to 1.3, greater than or equal to 1.4, greater than or equal to1.5, greater than or equal to 1.6, greater than or equal to 1.7, greaterthan or equal to 1.8, greater than or equal to 1.9, greater than orequal to 2, or greater than or equal to 2.1. In some embodiments, apolymer has an atomic ratio of fluorine to carbon of less than or equalto 2.2, less than or equal to 2.1, less than or equal to 2, less than orequal to 1.9, less than or equal to 1.8, less than or equal to 1.7, lessthan or equal to 1.6, less than or equal to 1.5, less than or equal to1.4, less than or equal to 1.3, or less than or equal to 1.2.Combinations of the above-referenced ranges are also possible (e.g.,greater than or equal to 1.1 and less than or equal to 2.2). Otherranges are also possible.

In some embodiments, a polymer deposited by a process described hereinmay undergo one or more further processes after deposition. As oneexample, in some embodiments, a fluorinated polymer deposited by aprocess described herein is annealed after being deposited. Annealingthe fluorinated polymer may comprise heating the fluorinated polymer.The temperature to which the fluorinated polymer, substrate, and/orenvironment in which the fluorinated polymer is positioned is heated tomay be greater than or equal to 50° C., greater than or equal to 75° C.,greater than or equal to 100° C., greater than or equal to 125° C.,greater than or equal to 150° C., greater than or equal to 175° C.,greater than or equal to 200° C., greater than or equal to 225° C.,greater than or equal to 250° C., greater than or equal to 275° C.,greater than or equal to 300° C., greater than or equal to 325° C.,greater than or equal to 350° C., or greater than or equal to 375° C.The temperature to which the fluorinated polymer, substrate, and/orenvironment in which the fluorinated polymer is positioned is heated tomay be less than or equal to 400° C., less than or equal to 375° C.,less than or equal to 350° C., less than or equal to 325° C., less thanor equal to 300° C., less than or equal to 275° C., less than or equalto 250° C., less than or equal to 225° C., less than or equal to 200°C., less than or equal to 175° C., less than or equal to 150° C., lessthan or equal to 125° C., less than or equal to 100° C., or less than orequal to 75° C. Combinations of the above-referenced ranges are alsopossible (e.g., greater than or equal to 50° C. and less than or equalto 400° C.). Other ranges are also possible.

An annealing step may be performed for a variety of suitable times. Insome embodiments, the annealing is performed for a period of time ofgreater than or equal to 30 minutes, greater than or equal to 1 hour,greater than or equal to 2 hours, greater than or equal to 5 hours,greater than or equal to 10 hours, greater than or equal to 15 hours,greater than or equal to 20 hours, greater than or equal to 24 hours, orgreater than or equal to 30 hours. In some embodiments, the annealing isperformed for a period of time of less than or equal to 48 hours, lessthan or equal to 30 hours, less than or equal to 24 hours, less than orequal to 20 hours, less than or equal to 15 hours, less than or equal to10 hours, less than or equal to 5 hours, less than or equal to 2 hours,or less than or equal to 1 hour. Combinations of the above-referencedranges are also possible (e.g., greater than or equal to 1 hour and lessthan or equal to 24 hours). Other ranges are also possible.

Fluorinated polymeric coatings may be annealed in a variety of suitableenvironments. In some embodiments, the annealing is performed in air. Itis also possible for the annealing to be performed in the presence of aninert gas (e.g., nitrogen, helium, argon). The annealing may beperformed inside the reaction volume and/or deposition chamber, and/ormay be performed after removal of a coated substrate from the reactionvolume and/or deposition chamber.

In some embodiments, the processes that are performed in a reactionvolume (e.g., polymerization, annealing, etc.) may be automated. Suchautomation may comprise providing software that reads instructions forthe various processes being performed (e.g., the flow rates and/or typesof gases introduced into the reaction system, the filament temperature,the temperature of the substrate, etc.) and then executes theseinstructions by directing further system components to carry them out.As one example, in some embodiments, software may read an excelspreadsheet including various system properties and the amount of timethe system should spend in various conditions and/or executing variousmethods. In some embodiments, instructions, like those provided by anexcel spreadsheet, may include instructions that arecondition-dependent. For instance, a set of instructions may require thesystem to be in a certain state and/or delay a certain process until oneor more properties of the reaction volume are within a certain range(e.g., the total pressure, the partial pressure of one or more gases,the filament temperature, the filament resistance). As one example, aset of instructions may comprise an instruction to delay theintroduction of monomers and/or precursors to monomers until thepressure in the reaction volume is below a set amount. As anotherexample, a set of instructions may comprise an instruction to determinethe resistance of the filament prior to the introduction of monomersand/or precursors to monomers and to decline to introduce the monomersand/or precursors to monomers if the resistance is outside of a setrange.

As described elsewhere herein, some embodiments relate to the depositionof fluorinated polymeric coatings and/or to fluorinated polymericcoatings. Further details regarding such coatings are provided below.

As one example of a coating property, in some embodiments, a coating isadhered to a substrate on which it is deposited. The strength ofadhesion between the coating and the substrate may be relatively strong.For instance, in some embodiments, a coating is adhered to a substratewith a strength of adhesion such that the adhesion score is greater thanor equal to 4. The adhesion score may be determined by the proceduredescribed in ASTM D3359.

As another example of a coating property, in some embodiments, a coatingmay cover a relatively large percentage of a surface of a substrate. Asan example, the coating may cover greater than or equal to 50%, greaterthan or equal to 75%, greater than or equal to 90%, greater than orequal to 95%, greater than or equal to 99%, greater than or equal to99.5%, greater than or equal to 99.8%, greater than or equal to 99.9%,or greater than or equal to 99.99% of the surface of the substrate. Insome embodiments, the coating covers less than or equal to 100%, lessthan or equal to 99.99%, less than or equal to 99.9%, less than or equalto 99.8%, less than or equal to 99.5%, less than or equal to 99%, lessthan or equal to 95%, less than or equal to 90%, or less than or equalto 75% of the surface of the substrate. Combinations of theabove-referenced ranges are also possible (e.g., greater than or equalto 50% and less than or equal to 100%). Other ranges are also possible.

As described elsewhere herein, some embodiments relate to the depositionof fluorinated polymeric coatings onto substrates and/or to substrateson which a fluorinated polymeric coating is disposed. Further detailsregarding such substrates are provided below.

The types of substrates that may be coated by the systems and methodsdescribed herein may generally be selected as desired. In someembodiments, the substrate comprises a polymeric material (e.g., aplastic, an elastomer). It is also possible for a substrate to be coatedto comprise a metal. The substrates may be a variety of suitablearticles, non-limiting examples of which include seals, gaskets,o-rings, and molds.

As described elsewhere herein, in some embodiments, a substratecomprises one or more depressions in its surface. The depressions mayhave any suitable depth. In some embodiments, a substrate comprisesdepressions having a depth of (and/or comprises depressions having anaverage depth of) greater than or equal to 0.1 inch, greater than orequal to 0.2 inches, greater than or equal to 0.25 inches, greater thanor equal to 0.3 inches, greater than or equal to 0.4 inches, greaterthan or equal to 0.5 inches, greater than or equal to 0.75 inches,greater than or equal to 1 inch, greater than or equal to 1.5 inches,greater than or equal to 2 inches, greater than or equal to 3 inches,greater than or equal to 4 inches, greater than or equal to 5 inches,greater than or equal to 7.5 inches, greater than or equal to 10 inches,greater than or equal to 12.5 inches, greater than or equal to 15inches, greater than or equal to 17.5 inches, or greater than or equalto 20 inches. In some embodiments, a substrate comprises depressionshaving a depth of (and/or comprises depressions having an average depthof) less than or equal to 24 inches, less than or equal to 20 inches,less than or equal to 17.5 inches, less than or equal to 15 inches, lessthan or equal to 12.5 inches, less than or equal to 10 inches, less thanor equal to 7.5 inches, less than or equal to 5 inches, less than orequal to 4 inches, less than or equal to 3 inches, less than or equal to2 inches, less than or equal to 1.5 inches, less than or equal to 1inch, less than or equal to 0.75 inches, less than or equal to 0.5inches, less than or equal to 0.4 inches, less than or equal to 0.3inches, less than or equal to 0.25 inches, or less than or equal to 0.2inches. Combinations of the above-referenced ranges are also possible(e.g., greater than or equal to 0.1 inch and less than or equal to 24inches, or greater than or equal to 0.1 inches and less than or equal to5 inches). Other ranges are also possible.

In some embodiments, a method comprises causing a substrate to undergoone or more processes prior to the deposition of a fluorinated polymericcoating thereon. One example of such a process is a cleaning process.The cleaning process may comprise removing one or more contaminants fromthe substrate and/or the substrate surface. The cleaning process maycomprise exposing the substrate to a fluid and then immersing and/orsoaking the substrate in the fluid, rinsing the substrate with a fluid,and/or sonicating the substrate in the presence of a fluid. In someembodiments, one or more of these processes is followed by an optionalheating step and/or an optional drying step (e.g., a drying step inwhich the substrate is exposed to nitrogen and/or vacuum). Non-limitingexamples of suitable fluids for such processes include organic solvents(e.g., isopropyl alcohol, acetone), water, and/or solutions comprisingan organic or aqueous solvent and a surfactant. The fluid to which thesubstrate is exposed may solubilize and/or suspend contaminants presenton the substrate and/or its surface, which may remove them therefrom.Another example of a suitable cleaning process comprises exposing thesubstrate to a plasma to remove contaminants (e.g., surfacecontaminant(s)) therefrom.

In some embodiments, a method comprises depositing a fluorinatedpolymeric coating on a substrate shortly after a cleaning process.Without wishing to be bound by any particular theory, it is believedthat doing so may be advantageous because it may prevent recontaminationof the substrate with contaminants present in the ambient environmentafter cleaning and prior to deposition of the fluorinated polymericcoating. Depositing a fluorinated polymeric coating on a substrateshortly after a cleaning process is also believed to prevent and/orreduce the amount of internal contaminants transported to the surface ofthe substrate after cleaning. For instance, it is believed that somesubstrates may comprise low molecular weight contaminants throughouttheir interiors (e.g., small molecules, oligomers, low molecular weightpolymers, processing aids, chemicals compounded with the substrate), andthat removing such contaminants from the surface may cause transport ofsuch contaminants over time from the substrate interiors to thesubstrate surfaces by diffusion. As low molecular weight contaminantspresent at the surface of a substrate are believed to disadvantageouslyinterfere with the adhesion between a fluorinated polymeric coatingdeposited thereon and the substrate, preventing such transport mayenhance the adhesion of the fluorinated polymeric coating to thesubstrate.

In some embodiments, a method comprises depositing a fluorinatedpolymeric coating on a substrate within 2 hours, within 1.5 hours,within 1.25 hours, within 1 hour, within 45 minutes, within 30 minutes,within 25 minutes, within 20 minutes, within 15 minutes, within 10minutes, or within 5 minutes after a cleaning process is performed. Thedelay between the cleaning process and the deposition of the fluorinatedpolymeric coating may be at least 0 minutes, at least 5 minutes, atleast 10 minutes, at least 15 minutes, at least 20 minutes, at least 25minutes, at least 30 minutes, at least 45 minutes, at least 1 hour, atleast 1.25 hours, or at least 1.5 hours. Combinations of theabove-referenced ranges are also possible (e.g., within a period of timebetween 0 minutes and 2 hours, or within a period of time between 0minutes and 30 minutes). Other ranges are also possible.

In some embodiments, a method may comprise treating a substrate surfaceprior to depositing a fluorinated polymeric coating thereon to promoteadhesion of the fluorinated polymeric coating thereto with an adhesionpromoter. In such embodiments, the adhesion promoter can bevapor-deposited in situ in the reaction volume prior to deposition ofthe fluorinated polymeric coating. Examples of suitable adhesionpromoters include 1H,1H,2H,2H-Perfluorodecyltriethoxysilane,1H,1H,2H,2H-Perfluorooctyltriethoxysilane, 1H,1H,2H,2H-Perfluoroalkyltriethoxysilane, perfluorooctyltriclorosilane, andall classes of vinyl silanes.

It is also possible for a substrate to be heated (e.g., to a temperatureof between 20° C. and 300° C.) and/or exposed to a source of vacuum(e.g., to bring the pressure in the environment surrounding thesubstrate to between 0.1 mTorr and 760 Torr) prior to depositing afluorinated polymeric coating thereon.

Some substrates may comprise one or more volatile components whenintroduced into a reaction volume. The volatile components may outgasduring deposition of a fluorinated polymer coating onto the substrate.In some embodiments, the amount of gas outgassed from the substrateduring the deposition of the fluorinated polymeric coating may berelatively high. Without wishing to be bound by any particular theory,it is believed that some features of the methods described herein mayfacilitate the deposition of fluorinated polymeric coatings havingadvantageous properties in the presence of an appreciable amount of gasoutgassed from a substrate.

As one example, it is believed that outgassing gases unreactive with theother gases present in the reaction volume may have small or no effectson the fluorinated polymeric coatings deposited on the substrate. Forinstance, outgassing gases unreactive with the monomers and/orprecursors to monomers reacting to form the fluorinated polymericcoating may be relatively benign, especially when the other gasespresent in the reaction volume are inert gases.

As another example, it is believed that outgassing gases in the presenceof a filament kept at a relatively low temperature may have small or noeffects on the fluorinated polymeric coatings deposited on thesubstrate, as a filament kept at a relatively low temperature may notprovide sufficient energy to catalyze a reaction of a gas outgassingfrom a substrate.

As a third example, it is believed that outgassing gases from asubstrate may have small or no effects on the fluorinated polymericcoatings deposited on the substrate when the outgassing occurs in thepresence of a large volume of other gases (e.g., a large volume ofmonomers, precursors to monomers, and/or inert gases) and/or at highflow rates of other gases (e.g., high flow rates of monomers, precursorsto monomers, and/or inert gases) through the reaction volume. In suchconditions, the gas outgassing from the substrate may make up arelatively small amount of the total amount of gas in the reactionvolume, and so may have a proportionately small effect on the reactionsoccurring therein.

Non-limiting examples of gases that may be outgassed from a substrateduring deposition of a fluorinated polymeric coating thereon includewater and air.

In some embodiments, gases outgassed from the substrate make up greaterthan or equal to 0.01 mol %, greater than or equal to 0.02 mol %,greater than or equal to 0.05 mol %, greater than or equal to 0.075 mol%, greater than or equal to 0.1 mol %, greater than or equal to 0.2 mol%, greater than or equal to 0.5 mol %, greater than or equal to 0.75 mol%, greater than or equal to 1 mol %, greater than or equal to 2 mol %,greater than or equal to 5 mol %, greater than or equal to 7.5 mol %,greater than or equal to 10 mol %, greater than or equal to 12.5 mol %,greater than or equal to 15 mol %, greater than or equal to 17.5 mol %,greater than or equal to 20 mol %, or greater than or equal to 22.5 mol% of the gases present in the reaction volume during the deposition ofthe coating. In some embodiments, gases outgassed from the substratemake up less than or equal to 25 mol %, less than or equal to 22.5 mol%, less than or equal to 20 mol %, less than or equal to 17.5 mol %,less than or equal to 15 mol %, less than or equal to 12.5 mol %, lessthan or equal to 10 mol %, less than or equal to 7.5 mol %, less than orequal to 5 mol %, less than or equal to 2 mol %, less than or equal to 1mol %, less than or equal to 0.75 mol %, less than or equal to 0.5 mol%, less than or equal to 0.2 mol %, less than or equal to 0.1 mol %,less than or equal to 0.075 mol %, less than or equal to 0.05 mol %, orless than or equal to 0.02 mol % of the gases present in the reactionvolume during the deposition of the coating. Combinations of theabove-referenced ranges are also possible (e.g., greater than or equalto 0.01 mol % and less than or equal to 25 mol %, or greater than orequal to 0.1 mol % and less than or equal to 10 mol %). Other ranges arealso possible.

Some embodiments may relate to methods in which the systems describedherein are maintained at or close to their optimal performance. It isalso possible for this performance to be maintained while simultaneouslyreducing the effort of the operators of the systems to do so. This maybe accomplished by use of automated software that records one or moreconditions of the system and then alerts the operator when one or moresuch conditions indicates that carrying out one or more maintenancesteps would improve system performance. Such system conditions mayinclude the amount of time required for exposure to a source of vacuumto cause the reaction volume to reach a desired pressure, the state ofany valves positioned between any sources and the reaction volume (e.g.,a valve, such as a throttle valve, positioned between a source of vacuumand the reaction volume), the amount of time since a prior maintenancestep, the amount of time the system has been employed to depositfluorinated polymeric coatings, the amount of gases that have passedthrough the system, the amount of time that one or more filament(s) havebeen resistively heated, etc.

While several embodiments of the present invention have been describedand illustrated herein, those of ordinary skill in the art will readilyenvision a variety of other means and/or structures for performing thefunctions and/or obtaining the results and/or one or more of theadvantages described herein, and each of such variations and/ormodifications is deemed to be within the scope of the present invention.More generally, those skilled in the art will readily appreciate thatall parameters, dimensions, materials, and configurations describedherein are meant to be exemplary and that the actual parameters,dimensions, materials, and/or configurations will depend upon thespecific application or applications for which the teachings of thepresent invention is/are used. Those skilled in the art will recognize,or be able to ascertain using no more than routine experimentation, manyequivalents to the specific embodiments of the invention describedherein. It is, therefore, to be understood that the foregoingembodiments are presented by way of example only and that, within thescope of the appended claims and equivalents thereto, the invention maybe practiced otherwise than as specifically described and claimed. Thepresent invention is directed to each individual feature, system,article, material, kit, and/or method described herein. In addition, anycombination of two or more such features, systems, articles, materials,kits, and/or methods, if such features, systems, articles, materials,kits, and/or methods are not mutually inconsistent, is included withinthe scope of the present invention.

All definitions, as defined and used herein, should be understood tocontrol over dictionary definitions, definitions in documentsincorporated by reference, and/or ordinary meanings of the definedterms.

The indefinite articles “a” and “an,” as used herein in thespecification and in the claims, unless clearly indicated to thecontrary, should be understood to mean “at least one.”

The phrase “and/or,” as used herein in the specification and in theclaims, should be understood to mean “either or both” of the elements soconjoined, i.e., elements that are conjunctively present in some casesand disjunctively present in other cases. Multiple elements listed with“and/or” should be construed in the same fashion, i.e., “one or more” ofthe elements so conjoined. Other elements may optionally be presentother than the elements specifically identified by the “and/or” clause,whether related or unrelated to those elements specifically identified.Thus, as a non-limiting example, a reference to “A and/or B”, when usedin conjunction with open-ended language such as “comprising” can refer,in one embodiment, to A only (optionally including elements other thanB); in another embodiment, to B only (optionally including elementsother than A); in yet another embodiment, to both A and B (optionallyincluding other elements); etc.

As used herein in the specification and in the claims, “or” should beunderstood to have the same meaning as “and/or” as defined above. Forexample, when separating items in a list, “or” or “and/or” shall beinterpreted as being inclusive, i.e., the inclusion of at least one, butalso including more than one, of a number or list of elements, and,optionally, additional unlisted items. Only terms clearly indicated tothe contrary, such as “only one of” or “exactly one of,” or, when usedin the claims, “consisting of,” will refer to the inclusion of exactlyone element of a number or list of elements. In general, the term “or”as used herein shall only be interpreted as indicating exclusivealternatives (i.e. “one or the other but not both”) when preceded byterms of exclusivity, such as “either,” “one of,” “only one of,” or“exactly one of.” “Consisting essentially of,” when used in the claims,shall have its ordinary meaning as used in the field of patent law.

As used herein in the specification and in the claims, the phrase “atleast one,” in reference to a list of one or more elements, should beunderstood to mean at least one element selected from any one or more ofthe elements in the list of elements, but not necessarily including atleast one of each and every element specifically listed within the listof elements and not excluding any combinations of elements in the listof elements. This definition also allows that elements may optionally bepresent other than the elements specifically identified within the listof elements to which the phrase “at least one” refers, whether relatedor unrelated to those elements specifically identified. Thus, as anon-limiting example, “at least one of A and B” (or, equivalently, “atleast one of A or B,” or, equivalently “at least one of A and/or B”) canrefer, in one embodiment, to at least one, optionally including morethan one, A, with no B present (and optionally including elements otherthan B); in another embodiment, to at least one, optionally includingmore than one, B, with no A present (and optionally including elementsother than A); in yet another embodiment, to at least one, optionallyincluding more than one, A, and at least one, optionally including morethan one, B (and optionally including other elements); etc.

It should also be understood that, unless clearly indicated to thecontrary, in any methods claimed herein that include more than one stepor act, the order of the steps or acts of the method is not necessarilylimited to the order in which the steps or acts of the method arerecited.

In the claims, as well as in the specification above, all transitionalphrases such as “comprising,” “including,” “carrying,” “having,”“containing,” “involving,” “holding,” “composed of,” and the like are tobe understood to be open-ended, i.e., to mean including but not limitedto. Only the transitional phrases “consisting of” and “consistingessentially of” shall be closed or semi-closed transitional phrases,respectively, as set forth in the United States Patent Office Manual ofPatent Examining Procedures, Section 2111.03.

1. A system, comprising: a deposition chamber comprising a reactionvolume; and a cooling element, wherein: the reaction volume is capableof comprising hexafluoropropylene oxide vapor and being evacuated of airby a source of vacuum; the reaction volume comprises a filament takingthe form of a wire configured to increase in temperature upon theapplication of a voltage thereto; the wire is configured to heat thehexafluoropropylene oxide vapor, thereby causing it to decompose; asubstrate is positioned in the reaction volume; the cooling element ispositioned around the substrate; and the cooling element extends from abottom of the substrate to the top of the substrate.
 2. A system,comprising: a deposition chamber comprising a reaction volume; and acooling element, wherein: the reaction volume is capable of comprisinghexafluoropropylene oxide vapor and being evacuated of air by a sourceof vacuum; the reaction volume comprises a filament taking the form of awire configured to increase in temperature upon the application of avoltage thereto; the wire is configured to heat the hexafluoropropyleneoxide vapor, thereby causing it to decompose; a substrate is positionedin the reaction volume; the cooling element is positioned around thesubstrate; and the substrate is freely-movable with respect to thecooling element.
 3. A method, comprising: polymerizinghexafluoropropylene oxide to form a particle comprisingpoly(tetrafluoroethylene); and depositing the particle comprisingpoly(tetrafluoroethylene) onto a surface, wherein: the polymerization isperformed in a reaction volume; the reaction volume is positioned in adeposition chamber; the reaction volume comprises at most 10 mTorr ofair and comprises hexafluoropropylene oxide vapor; the reaction volumecomprises a filament taking the form of a resistively heated wire; thewire heats the hexafluoropropylene oxide vapor, thereby causing it todecompose; and when the particle forms, it is surrounded by gas.
 4. Amethod, comprising: depositing a coating comprisingpoly(tetrafluoroethylene) on a substrate, wherein: the substrate ispositioned in a reaction volume; the reaction volume is positioned in adeposition chamber; the reaction volume comprises at most 10 mTorr ofair and comprises hexafluoropropylene oxide vapor; the reaction volumecomprises a filament taking the form of a resistively heated wire; thewire heats the hexafluoropropylene oxide vapor, thereby causing it todecompose; the substrate outgasses one or more gases during thedeposition of the coating; and the one or more gases make up greaterthan or equal to 0.1 mol % and less than or equal to 10 mol % of thegases present in the reaction volume during the deposition of thecoating.
 5. A method, comprising: removing contaminants from a surfaceof a substrate by immersing the substrate in a solvent; and within 30minutes after the contaminants are removed, depositing a coatingcomprising poly(tetrafluoroethylene) onto the surface of the substrateby chemical vapor deposition, wherein, during the deposition step: thesubstrate is positioned in a reaction volume; the reaction volume ispositioned in a deposition chamber; the reaction volume comprises atmost 10 mTorr of air and comprises hexafluoropropylene oxide vapor; thereaction volume comprises a filament taking the form of a resistivelyheated wire; and the wire heats the hexafluoropropylene oxide vapor,thereby causing it to decompose; and wherein, after the deposition step,the coating has an adhesion to the substrate such that its adhesionscore, as determined by the procedure described in ASTM D3359, isgreater than or equal to
 4. 6. The method of claim 3, wherein atemperature of the wire is greater than or equal to 150° C. and lessthan or equal to 1500° C.
 7. The method of claim 3, wherein an amount ofhexafluoropropylene oxide vapor in the reaction volume is greater thanor equal to 1 mol % and less than or equal to 100 mol % of the gasespresent in the reaction volume.
 8. The method of claim 3, wherein thereaction volume further comprises a carrier gas.
 9. The method of claim8, wherein the carrier gas is an inert gas.
 10. The method of claim 3,wherein a pressure of the reaction volume is greater than or equal to 1mTorr and less than or equal to 100 Torr.
 11. The method of claim 3,wherein the reaction volume comprises a plurality of filaments takingthe form of wires.
 12. The method of claim 3, wherein greater than orequal to 90% of the polymerization reaction results in the production ofparticles surrounded by gas.
 13. The system of claim 1, wherein thesubstrate comprises an elastomer.
 14. The system of claim 1, wherein thecooling element is cooled by the circulation of cooled fluid acrossand/or through the cooling element.
 15. The system of claim 1, whereinthe cooling element is positioned beneath the substrate.
 16. The methodof claim 3, wherein the particle has a diameter of greater than or equalto 0.5 nm and less than or equal to 50 microns.
 17. The method of claim3, wherein the particle has a diameter of greater than or equal to 1 nmand less than or equal to 1 micron.
 18. The system of claim 4, whereinthe gases outgassed by the substrate comprise water and/or air.
 19. Thesystem of claim 4, wherein the contaminants comprise small molecules,oligomers, low molecular weight polymers, processing aids, and/orchemicals compounded with the substrate.
 20. The system of claim 4,wherein the coating is deposited prior to appreciable transport ofcontaminants from an interior of the substrate to a surface of thesubstrate.